Compositions formed from hydroxyaluminoxane and their use as catalyst components

ABSTRACT

Surprisingly stable olefin polymerization co-catalysts formed from hydroxyaluminoxanes are revealed. In one embodiment of the invention, a solid composition of matter is formed from a hydroxyaluminoxane and a treating agent, whereby the rate of OH-decay for the solid composition is reduced as compared to that of the hydroxyaluminoxane. Processes for converting a hydroxyaluminoxane into a such a solid composition of matter, supported catalysts formed from such solid compositions of matter, as well as methods of their use, are described.

REFERENCE TO RELATED APPLICATIONS

This is a continuation-in-part of prior U.S. patent application Ser. No.09/655,218, filed Sep. 5, 2000, now U.S. Pat. No. 6,462,212, andincorporated herein by reference, which is a continuation-in-part ofU.S. patent application Ser. No. 09/177,736, filed on Oct. 23, 1998, nowU.S. Pat. No. 6,160,145, incorporated herein by reference. Thisapplication may be considered related to U.S. patent application Ser.No. 09/946,976, co-filed Sep. 5, 2001, now U.S. Pat. No. 6,492,292.

TECHNICAL FIELD

This invention relates to novel compositions of matter which are highlyeffective as catalyst components, and to the preparation and use of suchcompositions.

BACKGROUND

Partially hydrolyzed aluminum alkyl compounds known as aluminoxanes(a.k.a. alumoxanes) are effective in activating metallocenes forpolymerization of olefins. Activating effects of water in such systemswere initially noted by Reichert, et al. (1973) and Breslow, et al.(1975), and extended to trimethylaluminum-based systems by Sinn,Kaminsky, et al. (1976). Subsequent research by Sinn and Kaminskydemonstrated that this activation was due to formation ofmethylaluminoxane from partial hydrolysis of trimethylaluminum presentin the system. Methylaluminoxane. (a.k.a. methylalumoxane) has becomethe aluminum co-catalyst of choice in the industry.

Subsequent to the above original discoveries in this field, considerableworldwide effort has been devoted to improving the effectiveness ofcatalyst systems based on use of aluminoxanes or modified aluminoxanesfor polymerization of olefins and related unsaturated monomers.

Representative of many patents in the field of aluminoxane usage informing olefin polymerization catalyst systems with suitable metalcompounds is U.S. Pat. No. 5,324,800 to Welborn et al. which claims anoriginal filing date in 1983. This patent describes olefinpolymerization catalysts made from metallocenes of a metal of Groups 4b,5b, or 6b, and a cyclic or linear C₁-C₅ alkylaluminoxane. The cyclic andthe linear aluminoxanes are depicted, respectively, by the formulas(R—Al—O)_(n) and R(R—Al—O)_(n)AlR₂ where n is from 1 to about 20, and Ris most preferably methyl. The aluminoxanes are made by controlledhydrolysis of the corresponding aluminum trialkyl.

Another relatively early patent in the field, U.S. Pat. No. 4,752,597 toTurner based on a filing date of 1985, describes olefin polymerizationcatalysts comprising the reaction products of a metallocene complex ofgroup IVB, VB, VIB, and VII of the periodic table and an excess ofaluminoxane. These catalysts are formed by pre-reacting a metalloceneand an aluminoxane in mole ratios greater than 12:1, such as about 12:1to about 100:1, to produce a solid product which precipitates fromsolution. Despite assertions of suitable catalytic activity, in realitythe activity of these materials is so low as to be of no practicalimportance whatsoever.

In U.S. Pat. Nos. 4,960,878 and 5,041,584 to Crapo et al. modifiedmethylaluminoxane is formed in several ways. One involves reacting atetraalkyldialuminoxane, R₂Al—O—AlR₂, containing C₂ or higher alkylgroups with trimethylaluminum (TMA) at −10 to 150° C. Another involvesreacting TMA with a polyalkylaluminoxane (—Al(R)—O—)_(n) where R is C₂alkyl or higher and n is greater than 1, e.g., up to 50. Temperaturessuggested for this reaction are −20 to 50° C. A third way involvesconducting the latter reaction and then reacting the resultant product,which is indicated to be a complex between trimethylaluminum and thepolyalkylaluminoxane, with water. The patent states that thewater-to-aluminum ratios used to make the polyalkylaluminoxane reagenthave an effect on the activity of the final methylaluminoxane. On thebasis of ethylene polymerizations using zirconocene dichloride catalystand a complex of trimethylaluminum with polyisobutylaluminoxanesubsequently reacted with water (MMAO) as co-catalyst, it is indicatedin the patent that the highest polymerization activities were achievedwith MMAO co-catalyst prepared at H₂O/Al ratios of about 0.6 to about1.0 and Al/Zr ratios in the range of 10,000/1 to 400,000/1.

Various references are available indicating that isobutylaluminoxanesthemselves are relatively ineffective on their own as co-catalysts. Forexample, several other reactions of alkylaluminum compounds with waterare disclosed in U.S. Pat. Nos. 4,960,878 and 5,041,584. Thus in Example1 of these patents, DIBAL-O (tetraisobutyldialuminoxane), a commercialproduct, was prepared by reaction of water with triisobutylaluminum(TIBA) in heptane using a water/TIBA ratio of about 0.5, followed bysolvent stripping at 58-65° C. under vacuum. In Examples 3-6 of thepatents isobutylaluminoxane (IBAO) was prepared by controlled additionof water to a 25% solution of TIBA in toluene in the temperature rangeof 0-12° C., followed by heating to 70-80° C. to ensure completereaction and remove dissolved isobutane. H₂O/Al ratios used were 0.98,1.21, 1.14, and 0.88. IBAO was again made in a similar manner in Example52 of the patents. Here the H₂O/Al ratio was 0.70, and the product washeated at 75° C. And in Example 70 tri-n-butylaluminum (TNBA) in toluenewas treated at 0-10° C. with water followed by heating to 85° C.Ethylene polymerizations using zirconocene dichloride catalyst andvarious products from the foregoing Examples were conducted. Specificactivities (×10³ gPE/(gZr.atm C₂H₄.hr)) of the catalysts made withDIBAL-O from Ex. 1, IBAO from Ex. 3, and IBAO from Ex. 6 were,respectively, 4.1, 4.2, and 7.7, as compared to 1000 for the catalystmade using conventional MAO as the co-catalyst. The patents acknowledgethat tetraisobutyldialuminoxane (DIBAL-O) showed “poor polymerizationactivity”, and from the foregoing test results the same can be said toapply to IBAO.

WO 96/02580 to Dall'occo, et al. describes olefin polymerizationcatalysts made by contacting a metallocene of Ti, Zr, or Hf, anorganoaluminum compound having at least one specified hydrocarbonsubstituent on the β-carbon atom of an aliphatic group bonded to analuminum atom, and water. Various ways of bringing these componentstogether are suggested. Polymerizations described were carried out usingAl/Zr mole ratios ranging from 500 up to as high as 5000.

EP 0 277 004 to Turner, published in 1988, describes the successfulpreparation and use as catalysts composed of an ionic pair derived fromcertain metallocenes of Group 4, most preferablybis(cyclopentadienyl)zirconium dimethyl or bis(cyclopentadienyl)hafniumdimethyl, reacted with certain trisubstituted ammonium salts of asubstituted or unsubstituted aromatic boron compound, most preferablyN,N-dimethylanilinium tetra(pentafluorophenyl)boron. While EP 0 277 004mentions that compounds containing an element of Groups V-B, VI-B,VII-B, VIII, I-B, II-B, III-A, IV-A, and V-A may be used in forming thecatalysts, no specific compounds other than boron compounds areidentified. In fact, EP 0 277 004 appears to acknowledge inability toidentify specific compounds other than boron compounds by stating:“Similar lists of suitable compounds containing other metals andmetalloids which are useful as second components could be made, but suchlists are not deemed necessary to a complete disclosure.” See in thisconnection Hlatky, Turner and Eckman, J. Am. Chem. Soc., 1989, 111,2728-2729, and Hlatky and Upton, Macromolecules, 1996, 29, 8019-8020.

U.S. Pat. No. 5,153,157 to Hlatky and Turner states that its process “ispracticed with that class of ionic catalysts referred to, disclosed, anddescribed in European Patent Applications 277,003 and 277,004.” Theprocess of U.S. Pat. No. 5,153,157 involves forming an ionic catalystsystem from two components. The first is a bis(cyclopentadienyl)derivative of a Group V-B metal compound containing at least one ligandwhich will combine with the second component or portion thereof such asa cation portion thereof. The second component is referred to as an ionexchange compound comprising (1) a cation which will irreversibly reactwith a ligand of the Group IV-B metal compound and (2) a noncoordinatinganion which is bulky, labile, and stable. The second component, alsotermed an activator component, comprises compounds of Groups V-B, VI-B,VII-B, VIII, I-B, II-B, III-A, IV-A, and V-A identified by a generalformula. Besides referring to the boron compounds of EP 277,004, supra,such as tri(n-butylammonium)tetra(pentafluorophenyl)boron andN,N-dimethylanilinium tetra(pentafluorophenyl)boron as suitableactivators, the U.S. '157 patent teaches use of boron compounds having aplurality of boron atoms, and also trialkyl aluminum compounds, triarylaluminum compounds, dialkylaluminum alkoxides, diarylaluminum alkoxides,and analogous compounds of boron. Of the organoaluminum activatorstriethylaluminum and trimethylaluminum are specified as most preferred.The Examples show use of a catalyst system formed from (1) a solution ofbis(cyclopentadienyl)zirconium dimethyl or bis(cyclopentadienyl)hafniumdimethyl and N,N-dimethylanilinium tetra(pentafluorophenyl)borontogether with (2) triethylborane, triethylaluminum, tri-sec-butylborane,trimethylaluminum, and diethylaluminum ethoxide. In some cases thecatalyst formed from the metallocene and the N,N-dimethylaniliniumtetra(pentafluorophenyl)boron without use of a compound of (2) gave nopolymer at all under the polymerization conditions used.

U.S. Pat. No. 5,198,401 to Turner, Hlatky, and Eckman refers, in part,to forming catalyst compositions derived from certain metallocenes ofGroup 4, such as bis(cyclopentadienyl)zirconium dimethyl orbis(cyclopentadienyl)hafnium dimethyl, reacted with certaintrisubstituted ammonium salts of a substituted or unsubstituted aromaticboron compound, such as N,N-dimethylaniliniumtetra(pentafluorophenyl)boron or tributylammoniumtetra(pentafluorophenyl)boron as in EP 0 277 004. However here the anionis described as being any stable and bulky anionic complex having thefollowing molecular attributes: I) the anion should have a moleculardiameter about or greater than 4 angstroms; 2) the anion should formstable salts with reducible Lewis acids and protonated Lewis bases; 3)the negative charge on the anion should be delocalized over theframework of the anion or be localized within the core of the anion; 4)the anion should be a relatively poor nucleophile; and 5) the anionshould not be a powerful reducing or oxidizing agent. Anions of thistype are identified as polynuclear boranes, carboranes,metallacarboranes, polyoxoanions and anionic coordination complexes.Elsewhere in the patent it is indicated that any metal or metalloidcapable of forming a coordination complex which is resistant todegradation by water (or other Brønsted or Lewis acids) may be used orcontained in the second activator compound [the first activator compoundappears not to be disclosed]. Suitable metals of the second activatorcompound are stated to include, but not be limited to, aluminum, gold,platinum and the like. No such compound is identified. Again afterlisting boron compounds the statement is made that “Similar lists ofsuitable compounds containing other metals and metalloids which areuseful as second components could be made, but such lists are not deemednecessary to a complete disclosure.” In this connection, again noteHlatky, Turner and Eckman, J. Am. Chem. Soc., 1989, 111, 2728-2729, andHlatky and Upton, Macromolecules, 1996, 29, 8019-8020.

Despite the above and many other efforts involving aluminumco-catalysts, the fact remains that in order to achieve suitablecatalysis on a commercial basis, relatively high aluminum to transitionmetal ratios must be employed. Typically for optimal activity analuminum to metallocene ratio of greater than about 1000:1 is requiredfor effective homogeneous olefin polymerization. According toBrintzinger, et al., Angew. Chem. Int. Ed. Engl., 1995, 34 1143-1170:

“Catalytic activities are found to decline dramatically for MAOconcentrations below Al:Zr ratio roughly 200-300:1. Even at Al:Zr ratiosgreater than 1000:1 steady state activities increase with rising MAOconcentrations approximately as the cube root of the MAO concentration”.

This requirement of high aluminum loading is mainly caused by ametallocene activation mechanism in which generation of catalyticallyactive species is equilibrium driven. In this role MAO acts as a Lewisacid to remove by group transfer a leaving group X^(⊖) from thetransition metal. This forms a weakly-coordinating anion, MAO-X^(⊖), inthe corresponding transition metal cation. That is, in such systems thefollowing equilibrium exists:

The Lewis acid sites in MAO abstract a negatively charged leaving groupsuch as a methide group from the metallocene to form the catalyticallyactive ion pair. The activation process is reversible and K_(eq) istypically small. Thus the ion pair can return to its neutral precursorswhich are catalytically inactive. To overcome this effect, a largeexcess of MAO is required to drive the equilibrium to the right.

The high aluminum loadings required for effective catalysis in suchsystems result in the presence of significant levels ofaluminum-containing residues (“ash”) in the polymer. This can impair theclarity of finished polymers formed from such catalyst systems.

A further disadvantage of MAO is its limited solubility in paraffinichydrocarbon solvents. Polymer manufacturers would find it ofconsiderable advantage to have in hand aluminoxane and metallocene-basedmaterials having high paraffin solubility.

Still another disadvantage of MAO has been its relatively high cost. Forexample, in an article entitled “Economics is Key to Adoption ofMetallocene Catalysts” in the Sep. 11, 1995 issue of Chemical &Engineering News, Brockmeier of Argonne National Laboratory concludedthat “a reduction in costs or amount of MAO has the potential forgreatly reducing the costs to employ metallocene catalysts”.

Thus it would be of inestimable value to the art if away could be foundof providing catalyst components based on use of aluminoxanes that areeffective co-catalysts for use with transition metal compounds at muchlower aluminum:metal ratios than have been effective heretofore. Inaddition, the art would be greatly advanced if this could beaccomplished with aluminoxane compositions that are less expensive thanMAO, that have high solubility in paraffinic solvents and that producelower ash residues in the polymers.

The invention described and claimed in U.S. Pat. No. 6,160,145 is deemedto have fulfilled most, if not all, of the foregoing desirableobjectives. In brief summary, that invention makes it possible toprovide catalyst compositions in which a low cost co-catalyst can beemployed at very low Al loadings. Such catalyst compositions typicallyhave high solubility in paraffinic solvents. Moreover they yield reducedlevels of ash and result in improved clarity in polymers formed fromsuch catalyst compositions. Making all of this possible is the provisionof a compound which comprises (i) a cation derived from a transition,lanthanide or actinide metal compound, preferably a metallocene, by lossof a leaving group, and (ii) an aluminoxate anion (a.k.a. aluminoxanateanion) derived by transfer of a proton from a stable or metastablehydroxyaluminoxane to said leaving group. In contrast to aluminoxanesused prior to the Parent Application and acting as Lewis acids (Eq. 1),the present compositions utilize hydroxyaluminoxane species (HO-AO)acting as Brønsted acids. In the formation of such compounds, a cationis derived from the transition, lanthanide or actinide metal compound byloss of a leaving group, and this cation forms an ion pair with analuminoxate anion devoid of such leaving group. The leaving group istypically transformed into a neutral hydrocarbon thus rendering thecatalyst-forming reaction irreversible as shown in Equation 2:

Cp₂MXR+HO-AO→[Cp₂M-X]^(⊕)(O-AO)^(⊖)+RH  (Eq. 2)

Note the absence of the leaving group, X, in the anion OAO^(⊖) ascompared to the presence of X in the anion, (X-MAO)^(⊖), of Equation 1.

In many of the patents related to the use of aluminoxanes as metalloceneco-catalysts, rather broad and generalized assertions have beenroutinely made regarding aluminum-to-metallocene ratio, types of alkylaluminoxanes, and ratio of water to aluminum for forming aluminoxanes.However, there is no disclosure of any type that would suggest, letalone demonstrate, the use of an aluminoxane as a Brønsted acid toactivate metallocenes and related organometallic catalysts. There are,furthermore, no known prior teachings or descriptions of how to use analuminoxane as a Brønsted acid muchless that by so doing it would bepossible to reduce the ratio of aluminum to transition, lanthanide oractinide metal to an unprecedentedly low level.

In another of its embodiments the invention of U.S. Pat. No. 6,160,145provides a process which comprises contacting a transition, lanthanideor actinide metal compound having at least two leaving groups with ahydroxyaluminoxane in which at least one aluminum atom has a hydroxylgroup bonded thereto so that one of said leaving groups is lost. Asnoted above, during the formation of such compounds, an aluminoxateanion is formed that is devoid of the leaving group. Instead the leavinggroup is typically transformed into a neutral hydrocarbon so that thecatalyst forming reaction is irreversible.

Still another embodiment of the invention of U.S. Pat. No. 6,160,145 isa process of polymerizing at least one polymerizable unsaturatedmonomer, which process comprises contacting said monomer underpolymerization conditions with a compound which comprises a cationderived from a transition, lanthanide or actinide metal compound,preferably a metallocene, by loss of a leaving group and an aluminoxateanion derived by transfer of a proton from a stable or metastablehydroxyaluminoxane to said leaving group.

Other embodiments of the invention of U.S. Pat. No. 6,160,145 includecatalyst compositions in which a compound comprising a cation derivedfrom a transition, lanthanide or actinide metal compound, preferably ametallocene, by loss of a leaving group and an aluminoxate anion derivedby transfer of a proton from a stable or metastable hydroxyaluminoxaneto said leaving group is supported on a carrier.

As described in U.S. patent application Ser. No. 09/655,218, filed Sep.5, 2000 (hereinafter the “'218 application”), the catalyst compositionsdescribed in U.S. Pat. No. 6,160,145 and also herein can haveexceptional stability once recovered and maintained under suitableconditions in the absence of a solvent. The '218 application describesstorage of a solid catalyst of this type in a drybox at ambient roomtemperatures for a one-month period without loss of its catalyticactivity. In contrast, the same catalyst composition is relativelyunstable if left in the reaction solution or put in solution after ithas been removed from solution. The added features of this invention areto recover the catalyst composition (catalytic compound) after itspreparation, optionally subject the catalyst composition to one or morefinishing procedures and/or optionally mix the catalyst composition withone or more inert substances under suitable inert anhydrous conditions,and store the catalyst composition by itself, in supported form or as asolvent-free mixture with one or more inert substances under suitableconditions which minimize exposure to moisture and air (oxygen) as muchas reasonably possible.

Thus in one of the embodiments described in the '218 application is acompound which comprises a cation derived from d-block or f-block metalcompound by loss of a leaving group and an aluminoxate anion derived bytransfer of a proton from a stable or metastable hydroxyaluminoxane tosaid leaving group, wherein such compound is in undissolved form in adry, inert atmosphere or environment. Preferably the compound in suchatmosphere or environment is in isolated form or is in supported form ona catalyst support.

Another embodiment described in the '218 application is a compound whichcomprises a cation derived from a d-block or f-block metal compound byloss of a leaving group and an aluminoxate anion devoid of said leavinggroup, wherein the compound comprised of such cation and aluminoxateanion is in undissolved form in a dry, inert atmosphere or environment.Preferably the compound in such atmosphere or environment is in isolatedform or is in supported form on a catalyst support.

A further embodiment described in the '218 application is a compoundwhich comprises a cation derived from a d-block or f-block metalcompound by loss of a leaving group transformed into a neutralhydrocarbon, and an aluminoxate anion derived by loss of a proton from ahydroxyaluminoxane having, prior to said loss, at least one aluminumatom having a hydroxyl group bonded thereto, wherein the compoundcomprised of such cation and aluminoxate anion is in undissolved formexcept during one or more optional finishing procedures, if and when anysuch finishing procedure is performed. In addition, the compound is keptin a dry, inert atmosphere during a storage period. Preferably thecompound in such atmosphere or environment is in isolated form or is insupported form on a catalyst support.

The compounds of each of the above embodiments of the '218 applicationcan be used as a catalyst either in the solid state or in solution. Thestability of the compound when in solution is sufficient to enable thecompound to perform as a homogeneous catalyst.

Still another embodiment described in the '218 application is a processwhich comprises contacting a d-block or f-block metal compound having atleast two leaving groups with a hydroxyaluminoxane in which at least onealuminum atom has a hydroxyl group bonded thereto so that one of saidleaving groups is lost; recovering the resultant metal-containingcompound so formed; and storing such recovered compound (preferably inisolated form or in supported form on a catalyst support) in ananhydrous, inert atmosphere or environment. Such compound is maintainedin undissolved form except during one or more optional finishingprocedures, if and when any such finishing procedure is performed.

Also provided as another embodiment of the '218 application is a processwhich comprises donating a proton from an aluminoxane to a leaving groupof a d-block or f-block metal compound to form a compound composed of acation derived from said metal compound and an aluminoxate anion devoidof said leaving group; recovering the compound composed of such cationand aluminoxate anion; storing such recovered compound (preferably inisolated form or in supported form on a catalyst support) in ananhydrous, inert atmosphere or environment; and maintaining suchcompound in undissolved form except during one or more optionalfinishing procedures, if and when any such finishing procedure isperformed.

Another embodiment of the '218 application is a process which comprisesinteracting a d-block or f-block metal compound having two leavinggroups and a hydroxyaluminoxane having at least one aluminum atom thathas a hydroxyl group bonded thereto to form a compound composed of acation through loss of a leaving group which is transformed into aneutral hydrocarbon, and an aluminoxate anion derived by loss of aproton from said hydroxyaluminoxane; recovering the compound composed ofsuch cation and aluminoxate anion; storing such recovered compound(preferably in isolated form or in supported form on a catalyst support)in an anhydrous, inert atmosphere or environment; and maintaining suchcompound in undissolved form except during one or more optionalfinishing procedures, if and when any such finishing procedure isperformed.

Still other embodiments are described in the '218 application.

Notwithstanding all of the foregoing advances, the meta-stable nature ofthe hydroxy groups in the hydroxyaluminoxane species of aluminoxanes canhave an negative impact upon the shelf life of this species ofcompounds. Increasing the steric bulk of these compounds does appear toincrease the lifetime of their OH groups (see, e.g., FIG. 6), but notsufficiently to meet the anticipated needs of commercial applications.Storage of these compounds at low temperature, e.g., circa −10° C., cansignificantly increase the compound lifetime (see, e.g., FIG. 7), butcost and operational considerations of this technique also are less thatideal for commercial applications.

Accordingly, a need exists for a way to significantly increasing thelifetime of the OH groups in hydroxyaluminoxanes, preferably at or nearroom temperature. A need also exists for a facile way to employ olefinpolymerization catalysts while avoiding reactor fouling.

BRIEF SUMMARY OF THE INVENTION

The present invention is deemed to meet these and other needs in asurprisingly novel way. It has now been found that hydroxyaluminoxanescan be converted into novel, solid compositions of matter, so as todrastically increase the lifetime of the hydroxy group(s) in thecomposition (i.e., reduce the composition OH-decay rate), even at roomtemperature, while at the same time reducing, if not eliminating,reactor fouling.

Thus, one embodiment of this invention provides a composition in theform of one or more individual solids, which composition is formed fromcomponents comprised of (i) a hydroxyaluminoxane and (ii) a carriermaterial compatible with said hydroxyaluminoxane and in the form of oneor more individual solids, said composition having a reduced OH-decayrate relative to the OH-decay rate of (i).

This invention also provides in another embodiment a composition whichcomprises a hydroxyaluminoxane supported on a solid support.

Yet another embodiment of the present invention is a process comprisingconverting a hydroxyaluminoxane into a composition in the form of one ormore individual solids by bringing together (i) a hydroxyaluminoxane and(ii) a carrier material compatible with said hydroxyaluminoxane and inthe form of one or more individual solids, whereby the rate of OH-decayfor said composition is reduced relative to the rate of OH-decay of (i).

Still another embodiment of the present invention is a supportedactivated catalyst composition formed by bringing together (A) acomposition in the form of one or more individual solids, whichcomposition is formed from components comprised of (i) ahydroxyaluminoxane and (ii) a carrier material compatible with saidhydroxyaluminoxane and in the form of one or more individual solids,said composition of (A) having a reduced OH-decay rate relative to theOH-decay rate of (i); and (B) a d- or f-block metal compound having atleast one leaving group on a metal atom thereof.

This invention also provides a process of preparing a supportedactivated catalyst, which process comprises bringing together (A) acomposition in the form of one or more individual solids formed bybringing together (i) a hydroxyaluminoxane and (ii) a carrier materialcompatible with said hydroxyaluminoxane and in the form of one or moreindividual solids, whereby the rate of OH-decay for said composition isreduced relative to the rate of OH-decay of (i); and (B) a d- or f-blockmetal compound having at least one leaving group on a metal atomthereof.

In another embodiment of this invention, an olefin polymerizationprocess is provided which comprises bringing together in apolymerization reactor or reaction zone (1) at least one polymerizableolefin and (2) a supported activated catalyst composition which is inaccordance with this invention.

Still another embodiment of this invention is a catalyst compositionformed by bringing together (A) a hydroxyaluminoxane and (B)rac-ethylenebis(1-indenyl)zirconium dimethyl.

A further embodiment of the invention provides a process for theproduction of a supported hydroxyaluminoxane which comprises bringingtogether (i) an aluminum alkyl in an inert solvent, (ii) a water source,and (iii) a carrier material, under hydroxyaluminoxane-forming reactionconditions.

Still another embodiment is a method of forming an olefin polymerizationcatalyst, which method comprises introducing into a reactor or areaction zone (A) a hydroxyaluminoxane and (B) a d- or f-block metalcompound in proportions such that an active olefin polymerizationcatalyst is formed. In this embodiment, the hydroxyaluminoxanepreferably is fed in the form of (i) a solution of thehydroxyaluminoxane in an inert solvent or in a liquid polymerizableolefinic monomer, or both; (ii) a slurry of the hydroxyaluminoxane in aninert diluent or in a liquid polymerizable olefinic monomer; (iii)unsupported solid particles; or (iv) one or more solids on a carriermaterial or catalyst support; or (v) any combination of two or more of(i), (ii), (iii), and (iv). More preferably, the hydroxyaluminoxane willbe fed in the form of one or more solids on a carrier material suspendedin an inert viscous liquid, e.g., mineral oil. Similarly, the d- orf-block metal compound preferably is fed in the form of (i) undilutedsolids or liquid, or (ii) a solution or slurry of the d- or f-blockmetal compound in an inert solvent or diluent, or in a liquidpolymerizable olefinic monomer, or in a mixture of any of these. Morepreferably, the d- or f-block metal compound will be fed in the form ofa solution or slurry of the metal compound in an inert solvent ordiluent. It is also preferred that the catalyst be formed from onlycomponents (A) and (B). The introduction of (A) and (B) into the reactoror reaction zone can proceed in any given order or sequence, or canproceed concurrently. Also, the introduction of (A) and (B) into thereactor or reaction zone can proceed continuously or intermittently.Preferably, the metal compound is fed into the hydroxyaluminoxane, andmore preferably the metal compound in the form of a solution or slurryin an inert solvent or diluent will be fed to the hydroxyaluminoxane inthe form of one or more solids on a carrier material suspended in aninert viscous liquid.

As another of its embodiments, this invention also provides, in aprocess for the catalytic polymerization of at least one olefin in apolymerization reaction vessel or reaction zone, the improvement whichcomprises introducing into the reaction vessel or reaction zone catalystcomponents comprising (A) a hydroxyaluminoxane and (B) a d- or f-blockmetal compound, in proportions such that said at least one olefin ispolymerized. Components (A) and (B) can be introduced into thepolymerization reactor vessel or zone as separate feeds, eithercontinuously or intermittently, and either concurrently or in anysequence. Alternatively, they can be brought together and allowed tointeract with each other for a suitable period of time with theresultant composition then being introduced into the polymerizationreactor or zone. Other polymerization components, e.g., aluminum alkyl,ordinary hydroxyaluminoxane, etc., can be introduced before, during, orafter the introduction of (A) and (B) or either of them or of apreformed catalyst formed by interaction between (A) and (B). The formsin which the hydroxyaluminoxane and the d- or f-block metal compound arefed into the polymerization reactor or zone can be any of thosedescribed in the immediately preceding paragraph.

The above and other embodiments, features, and advantages of thisinvention will become still further apparent from the ensuingdescription and appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an infrared spectrum of hydroxyisobutylaluminoxane (HO-IBAO)useful in the practice of this invention.

FIG. 2 is a superimposed series of infrared spectra of HO-IBAOillustrating the loss of hydroxyl groups at intervals during a two-dayperiod at ambient temperature.

FIG. 3 is a superimposed series of infrared spectra, the top spectrumbeing that of a fresh HO-IBAO, the middle spectrum being that of thesame HO-IBAO but taken 30 minutes later, and the bottom spectrum beingthat a catalyst composition of this invention formed from the reactionbetween rac-dimethylsilylbis(2-methylindenyl)zirconium dimethyl (MET-A)and HO-IBAO showing that the activation of a metallocene having asuitable leaving group is accompanied by a rapid loss of hydroxylgroups, consistent with HO-IBAO functioning as a Brønsted acid inmetallocene activation.

FIG. 4 are superimposed UV-Vis spectra, the top spectrum being that ofMET-A, the middle spectrum being that of a catalyst composition of thisinvention having an Al/Zr ratio of 21/1 formed from the reaction betweenMET-A and HO-IBAO, and the bottom spectrum being that of a catalystcomposition of this invention having an Al/Zr ratio of 11/1 formed fromthe reaction between MET-A and HO-IBAO.

FIG. 5 are superimposed UV-Vis spectra, the top spectrum being that ofMET-A, the middle spectrum being that of a composition formed from MET-Aand isobutylaluminoxane (IBAO) that resulted from loss or depletion ofhydroxyl groups from IBAO, and the bottom spectrum being that oftetraisobutyldialuminoxane (TIBAO).

FIG. 6 is a graph illustrating the change in infrared —OH absorptionover time at room temperature for HO-IBAO and forhydroxyisooctylaluminoxane (HO-IOAO).

FIG. 7 is a graph illustrating the change in infrared—OH absorption overtime at −10° C. for HO-IBAO and for HO-IOAO.

FIG. 8 is a DRIFTS subtraction spectrum of DO-IBAO/silica andHO-IBAO/silica.

FIG. 9 is a H¹-nmr spectrum of the distillate fromBnMgCl+DO-IBAO/silica.

FIG. 10 is a graph illustrating the change in the number of OH groupsper 100 Aluminum atoms overtime at room temperature for HO-IBAO at −10°C., HO-IBAO/silica(1) and HO-IBAO/silica(2).

FURTHER DETAILED DESCRIPTION OF THE INVENTION

Hydroxyaluminoxane Reactants

Unlike catalyst compositions formed from a transition, lanthanide oractinide metal compound (hereinafter “d- or f-block metal compound”) andMAO or other previously recognized aluminoxane co-catalyst species, thecatalyst compositions of U.S. Pat. No. 6,160,145 and U.S. patentapplication Ser. No. 09/655,218 are formed from a hydroxyaluminoxane.The hydroxyaluminoxane has a hydroxyl group bonded to at least one ofits aluminum atoms. To form these hydroxyaluminoxanes, a sufficientamount of water is reacted with an alkyl aluminum compound to result information of a compound having at least one HO—Al group and havingsufficient stability to allow reaction with a d- or f-blockorganometallic compound to form a hydrocarbon.

The alkyl aluminum compound used in forming the hydroxyaluminoxanereactant can be any suitable alkyl aluminum compound other thantrimethylaluminum. Thus at least one alkyl group has two or more carbonatoms. Preferably each alkyl group in the alkyl aluminum compound has atleast two carbon atoms. More preferably each alkyl group has in therange of 2 to about 24, and still more preferably in the range of 2 toabout 16 carbon atoms. Particularly preferred are alkyl groups that havein the range of 2 to about 9 carbon atoms each. The alkyl groups can becyclic (e.g., cycloalkyl, alkyl-substituted cycloalkyl, orcycloalkyl-substituted alkyl groups) or acyclic, linear or branchedchain alkyl groups. Preferably the alkyl aluminum compound contains atleast one, desirably at least two, and most preferably three branchedchained alkyl groups in the molecule. Most preferably each alkyl groupof the aluminum alkyl is a primary alkyl group, i.e., the alpha-carbonatom of each alkyl group carries two hydrogen atoms.

Suitable aluminum alkyl compounds which may be used to form thehydroxyaluminoxane reactant include dialkylaluminum hydrides andaluminum trialkyls. Examples of the dialkylaluminum hydrides includediethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminumhydride, di(2,4,4-trimethylpentyl)aluminum hydride,di(2-ethylhexyl)aluminum hydride, di(2-butyloctyl)aluminum hydride,di(2,4,4,6,6-pentamethylheptyl)aluminum hydride,di(2-hexyldecyl)aluminum hydride, dicyclopropylcarbinylaluminum hydride,dicyclohexylaluminum hydride, dicyclopentylcarbinylaluminum hydride, andanalogous dialkylaluminum hydrides. Examples of trialkylaluminumcompounds which may be used to form the hydroxyaluminoxane includetriethylaluminum, tripropylaluminum, tributylaluminum,tripentylaluminum, trihexylaluminum, triheptylaluminum,trioctylaluminum, and their higher straight chain homologs;triisobutylaluminum, tris(2,4,4-trimethylpentyl)aluminum,tri-2-ethylhexylaluminum, tris(2,4,4,6,6-pentamethylheptyl)aluminum,tris(2-butyloctyl)aluminum, tris(2-hexyldecyl)aluminum,tris(2-heptylundecyl)aluminum, and their higher branched chain homologs;tri(cyclohexylcarbinyl)aluminum, tri(2-cyclohexylethyl)aluminum andanalogous cycloaliphatic aluminum trialkyls. Triisobutylaluminum hasproven to be an especially desirable alkyl aluminum compound forproducing a hydroxyaluminoxane.

To prepare the hydroxyaluminoxane a solution of the alkyl aluminumcompound in an inert solvent, preferably a saturated or aromatichydrocarbon, is treated with controlled amounts of water whilemaintaining the vigorously agitated reaction mixture at low temperature,e.g., below about 0° C. When the exothermic reaction subsides, thereaction mixture is stored at a low temperature, e.g., below about 0° C.until used in forming a compound of this invention. When preparing ahydroxyaluminoxane from a low molecular weight alkylaluminum compound,the reaction mixture can be subjected, if desired, to stripping undervacuum at a temperature below room temperature to remove some loweralkane hydrocarbon co-product formed during the reaction. However, suchpurification is usually unnecessary as the lower alkane co-product ismerely an innocuous impurity.

Among suitable procedures for preparing hydroxyaluminoxanes for use inpractice of this invention, is the method described by Ikonitskii etal., Zhurnal Prikladnoi Khimii, 1989, 62(2). 394-397; and the Englishlanguage translation thereof available from Plenum PublishingCorporation, copyright 1989, as Document No. 0021-888X/89/6202-0354.

It is very important to slow down the premature loss of its hydroxylgroup content sufficiently to maintain a suitable level of OH groupsuntil the activation reaction has been effected. One way to accomplishthis is to maintain the temperature of the hydroxyaluminoxane productsolution sufficiently low. This is demonstrated by the data presentedgraphically in FIG. 2 which shows the loss of hydroxyl groups fromhydroxyisobutylaluminoxane at ambient room temperature in an IR cell.If, on the other hand, the same hydroxyaluminoxane solution is stored ina freezer at −10° C., the rate of hydroxyl group loss is reduced to sucha degree that the time scale for preserving the same amount of hydroxylgroups can be lengthened from one to two hours at ambient roomtemperature to one to two weeks at −10° C. If the hydroxyl group contentis lost, the compound reverts to an aluminoxane which is incapable offorming the novel ionic highly active catalytic compounds of thisinvention.

It is also important when preparing the hydroxyaluminoxanes to useenough water to produce the hydroxyaluminoxane, yet not so much water aswill cause its destruction. Typically the water/aluminum mole ratio isin the range of about 0.5/1 to about 1.2/1, and preferably in the rangeof 0.8/1 to 1.1/1. At least in the case of hydroxyisobutylaluminoxane,these ratios typically result in the formation of hydroxyaluminoxanehaving at least about one hydroxyl group for every seven aluminum atomsin the overall product. The hydroxyisobutylaluminoxane is essentiallydevoid of unreacted triisobutylaluminum.

However, it now has been discovered that the rate of OH-decay (i.e., therate at which OH groups disassociate so as to reduce the number of OHgroups present in the molecule) for the above-describedhydroxyalumioxane may be drastically and surprisingly reduced byconverting hydroxyaluminoxane into a composition in the form of one ormore individual solids having an OH-decay rate which is reduced relativeto the OH-decay rate of the hydroxyaluminoxane. Such a composition isformed by bringing together the hydroxyaluminoxane and a carriermaterial which is compatible with the hydroxyaluminoxane and which is inthe form of one or more individual solids. In bringing these twocomponents together, it is preferred that the hydroxyaluminoxane becomessupported upon the carrier material. Typically, the rate of OH-decay forthe composition so formed is reduced by a factor of at least 5, and morepreferably at least 10, as compared to the rate of OH-decay of thehydroxyaluminoxane. The composition formed from the hydroxyaluminoxaneand carrier material itself may be used to form active polymerizationcatalysts of this invention. Such compositions remain active as aBrønsted acid for a surprisingly greater period of time as compared tothat of the hydroxyaluminoxane.

When it is stated herein that the composition so formed or the carriermaterial is “in the form of one or more individual solids,” it is meantthat the composition or carrier material, as the case may be, is solidmatter, regardless of whether it takes the form of a single solid slabor unitary piece of matter in solid form, or the form of a mass made upof a plurality of unitary pieces of matter in solid form, e.g.,particles, pellets, micropellets, beads, crystals, agglomerates, etc. orthe form of some other macromolecular structure. Preferably, the carriermaterial is in particulate form, and more preferably is in particulateform having a surface area of typically at least about 20, preferably atleast about 30, and most preferably from at least about 50 m²/g, whichsurface area can range typically from about 20 to about 800, preferablyfrom about 30 to about 700, and most preferably from about 50 to about600 m²/g. It is also preferred that the carrier material particulatehave a bulk density of typically at least about 0.15, preferably atleast about 0.20, and most preferably at least about 0.25 g/ml, whichbulk density can range typically from about 0.15 to about 1, preferablyfrom about 0.20 to about 0.75, and most preferably from about 0.25 toabout 0.45 g/ml. Preferably, the carrier particulate has an average porediameter of typically from about 30 to about 300, and most preferablyfrom about 60 to about 150 Angstroms. The carrier particulate alsopreferably has a total pore volume of typically about 0.10 to about 2.0,more preferably from about 0.5 to about 1.8, and most preferably fromabout 0.8 to about 1.6 cc/g. The average particle size and itsdistribution will be dictated and controlled by the type ofpolymerization reaction contemplated for the catalyst composition. As ageneralization, the average particle size will be in the range of fromabout 4 to about 250, and preferably in the range of about 8 to about100 microns. However, with respect to specific processes, solutionpolymerization processes, for example, typically can employ an averageparticle size in the range of about 1 to about 10 microns, while acontinuous stirred tank reactor slurry polymerization typically canemploy an average particle size in the range of about 8 to about 50microns, a loop slurry polymerization typically can employ an averageparticle size in the range of about 10 to about 150 microns, and a gasphase polymerization typically can employ an average particle size inthe range of about 20 to about 120 microns. Other sizes may also bepreferred under varying circumstances. When the carrier material isformed by spray drying, it is also preferable that typically at least80, more preferably at least 90, and most preferably at least 95 vol.percent of that fraction of the carrier particles smaller than the D₉₀of the entire carrier particulate particle size distribution possessesmicrospheroidal shape (i.e., morphology). Also, when it is said that thecarrier material is “compatible” with the hydroxyaluminoxane, it ismeant that the carrier material is capable of coming into proximity orcontact with, or being mixed with or otherwise placed in the presenceof, the hydroxyaluminoxane without adversely affecting the ability ofthe hydroxyaluminoxane to activate the metal compound elsewheredescribed herein to form the polymerization catalysts of this invention.

The carrier material used in the practice of this invention ispreferably a solid support. Non-limiting examples of such solid supportswill include particulate inorganic catalyst supports such as, e.g.,inorganic oxides (e.g., silica, silicates, silica-alumina, alumina)clay, clay minerals, ion exchanging layered compounds, diatomaceousearth, zeolites, magnesium chloride, talc, and the like, includingcombinations of any two or more of the same, and particulate organiccatalyst supports such as, e.g., particulate polyethylene, particulatepolypropylene, other polyolefin homopolymers or copolymers, and thelike, including combinations of any two or more of the same. Particulateinorganic catalyst supports are preferred. It is also preferred that thesupport be anhydrous or substantially anhydrous. More preferred isparticulate calcined silica, which is optionally pretreated inconventional manner with a suitable aluminum alkyl, e.g., triethylaluminum. In certain applications, it may be preferred to suspend thecarrier material in a viscous inert liquid, e.g., mineral oil. Theviscosity of such inert liquid can vary depending upon the carriermaterial involved, but such viscous inert material is most preferablyviscous enough to retain the carrier material (and any materialsupported thereupon) in suspension over a desired period of time or atleast to permit of resuspension of the support (and any materialsupported thereupon) with agitation (e.g., stirring) after settling.Exemplary viscous inert liquid will preferably have a viscosity in therange of about 1 to about 2000 centipoise, and more preferably in therange of about 200 to about 1500 centipoise, at ambient temperature.

The amount of hydroxyaluminoxane in the composition which includes acarrier material typically will be about 5 to about 50 weight percent,preferably about 10 to about 40 weight percent, and more preferablyabout 20 to about 30 weight percent, hydroxyaluminoxane based upon thetotal weight of the composition, with the balance being made up of thecarrier material.

The reaction conditions under which the carrier material and thehydroxyaluminoxane may be brought together may vary widely, buttypically will be characterized with a temperature in the range of about−20 to about 100° C., using superatmospheric, subatmospheric oratmospheric pressure (so long as the desired product is formed) and aninert atmosphere or environment. These components may be broughttogether in any of a variety of ways, including, e.g., by feeding thehydroxyaluminoxane and the carrier material concurrently or sequentiallyin any sequence, and mixing the components together, preferably in aninert liquid medium, or by otherwise mixing or contacting thesecomponents with each other, again preferably in an inert liquid medium.The liquid medium can be separately fed to the mixing vessel before,during, and/or after feeding or otherwise introducing thehydroxyaluminoxane and/or the carrier material. Similarly, thehydroxyaluminoxane can be fed as a solution or slurry in the liquidmedium, and/or, the carrier material when in particulate form can be fedas a slurry in the liquid medium to thereby provide all or a part of thetotal liquid medium being used. Such procedures can be conducted eitherin batch, continuously or intermittently. Preferably, the carriermaterial and the hydroxyaluminoxane will be brought together in thepresence of an inert solvent in which the hydroxyaluminoxane isdissolved, e.g., in an inert organic solvent such as a saturatedaliphatic or cycloaliphatic hydrocarbon, or an aromatic hydrocarbon, ora mixture of any two or more such hydrocarbons.

For quantitative purposes with respect to the number of hydroxyl groupspresent in the hydroxyaluminoxane or in the composition made therefrom,a deuterium-labeled DO-hydroxyaluminoxane/carrier preferably is usedwhen the carrier material includes hydroxyl groups (e.g., silica).Typically, samples will be stored at room temperature in a dry box andsampled periodically for quantitative analysis to determine the rate ofOH-decay at given points in time. A typical procedure with respect todeuterium-labeled hydroxyisobutylaluminoxane/silica is described belowin Example 28. This procedure will preferably be employed to quantifythe hydroxyl groups (as DO- per 100 aluminum atoms) present in thecomposition at or near the time of fresh preparation (i.e., time zero),and at one or more intervals of time thereafter, preferably at 48 hoursor more preferably at 72 hours following preparation of the samplematerials. The change in the number of hydroxyl groups at the selectedtime interval from that at time zero, divided by the amount of time,will be the OH-decay rate. When the carrier material does not includehydroxyl groups, or when the sample material is unsupportedhydroxyaluminoxane, this same procedure may be employed but withoutdeuterium labeling.

These co-catalyst compositions formed from the hydroxyaluminoxane andthe carrier material may be formed and isolated prior to use as acatalyst component, or they may be formed in situ, such as, e.g., duringthe process of production of the hydroxyaluminoxane itself. Accordingly,these compositions may be formed by addition of the carrier materialduring the synthesis of hydroxyaluminoxane. Thus, for example, thecarrier material may be introduced at any point during the synthesisprocesses described hereinabove for the hydroxyaluminoxane, so as tobring an aluminum alkyl in solution together with a water source and thecarrier material under hydroxyaluminoxane-forming reaction conditions.Besides free water, other non-limiting examples of a suitable watersource include hydrates of alkali or alkaline earth metal hydroxidessuch as, for example, lithium, sodium, potassium, barium, calcium,magnesium, and cesium hydroxides (e.g., sodium hydroxide mono- anddihydrate; barium hydroxide octahydrate, potassium hydroxide dihydrate,cesium hydroxide monohydrate, lithium hydroxide monohydrate, and thelike), aluminum sulfate, certain hydrated catalyst support materials(e.g., un-dehydrated silica), as well as mixtures of any two or more ofthe foregoing. The reaction conditions for this in situ formation willtypically be the same as those reactions conditions taught herein forforming the hydroxyaluminoxane generally.

When forming co-catalyst compositions from the hydroxyaluminoxane andthe carrier material, it is preferred that the hydroxyaluminoxane haveless than 25 OH groups per 100 aluminum atoms, and even more preferredthat they have no more than 15 OH groups per 100 aluminum atoms. Incertain other embodiments of this invention, it is also preferred thatthe composition so made be substantially insoluble in an inert organicsolvent such as various hydrocarbons, e.g., saturated aliphatic orcycloaliphatic hydrocarbons.

These compositions formed from a hydroxyaluminoxane may be employed asthe olefin polymerization co-catalyst in place of the less stablehydroxyaluminoxane, to provide a surprisingly more stable yet equallyeffective co-catalyst and catalyst composition in commercialapplications.

d- or f-Block Metal Compound

Various d- and f-block metal compounds may be used in forming thecatalytically active compounds of this invention. The d-block andf-block metals of this reactant are the transition, lanthanide andactinide metals. See, for example, the Periodic Table appearing on page225 of Moeller, et al., Chemistry, Second Edition, Academic Press,Copyright 1984. As regards the metal constituent, preferred arecompounds of Fe, Co, Pd, and V. More preferred are compounds of themetals of Groups 4-6 (Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and W), and mostpreferred are the Group 4 metals, especially hafnium, and mostespecially zirconium.

A vital feature of the d- or f-block metal compound used in forming theionic compounds of this invention is that it must contain at least oneleaving group that forms a separate co-product by interaction with aproton from the hydroxyaluminoxane or that interacts with a proton fromthe hydroxyaluminoxane so as to be converted from a cyclic divalentgroup into an open chain univalent group bonded to the metal atom of themetallocene. Thus the activity of the chemical bond between the d- orf-block metal atom and the leaving group must be at least comparable toand preferably greater than the activity of the aluminum-carbon bond ofthe hydroxyaluminoxane. In addition, the basicity of the leaving groupmust be such that the acidity of its conjugate acid is comparable to orless than the acidity of the hydroxyaluminoxane. Univalent leavinggroups that meet these criteria include hydride, hydrocarbyl andsilanylcarbinyl (R₃SiCH₂—) groups, such as methyl, ethyl, vinyl, allyl,cyclohexyl, phenyl, benzyl, trimethylsilanylcarbinyl, amido, alkylamido,substituted alkylamido, etc. Of these, the methyl group is the mostpreferred leaving group. Suitable divalent cyclic groups that can serveas leaving groups by a ring opening mechanism whereby a cyclic group isconverted into an open chain group that is still bonded to the metalatom of the metallocene include conjugated diene divalent anionic ligandgroups such as a conjugated diene or a hydrocarbyl-, halocarbyl-, orsilyl substituted derivative thereof, such conjugated diene anionicligand groups having from 4 to about 40 nonhydrogen atoms and beingcoordinated to the metal atom of the metallocene so as to form ametallocyclopentene therewith. Typical conjugated diene ligands of thistype are set forth for example in U.S. Pat. No. 5,539,068.

Metallocenes make up a preferred class of d- and f-block metal compoundsused in making the ionic compounds of this invention. These compoundsare characterized by containing at least one cyclopentadienyl moietypi-bonded to the metal atom. For use in this invention, the metallocenemust also have bonded to the d- or f-block metal atom at least oneleaving group capable of forming a stable co-product on interaction witha proton from the hydroxyaluminoxane. A halogen atom (e.g., a chlorineatom) bonded to such metal atom is incapable of serving as a leavinggroup in this regard in as much as the basicities of such halogen atomsare too low.

Such leaving groups may be prepared separately or in situ. For example,metallocene halides may be treated with alkylating agents such asdialkylaluminum alkoxides to generate the desired alkylmetallocene insitu. Reactions of this type are described for example in WO 95/10546.

Metallocene structures in this specification are to be interpretedbroadly, and include structures containing 1, 2, 3 or 4 Cp orsubstituted Cp rings. Thus metallocenes suitable for use in thisinvention can be represented by the Formula I:

B_(a)CP_(b)ML_(c)X_(d)  (I)

where Cp independently in each occurrence is acyclopentadienyl-moiety-containing group which typically has in therange of 5 to about 24 carbon atoms; B is a bridging group or ansa groupthat links two Cp groups together or alternatively carries an alternatecoordinating group such as alkylaminosilylalkyl, silylamido, alkoxy,siloxy, aminosilylalkyl, or analogous monodentate hetero atom electrondonating groups; M is a d- or f-block metal atom; each L is,independently, a leaving group that is bonded to the d- or f-block metalatom and is capable of forming a stable co-product on interaction with aproton from a hydroxyaluminoxane; X is a group other than a leavinggroup that is bonded to the d- or f-block metal atom; a is 0 or 1; b isa whole integer from 1 to 3 (preferably 2); c is at least 2; d is 0or 1. The sum of b, c, and d is sufficient to form a stable compound,and often is the coordination number of the d- or f-block metal atom.

Cp is, independently, a cyclopentadienyl, indenyl, fluorenyl or relatedgroup that can π-bond to the metal, or a hydrocarbyl-, halo-,halohydrocarbyl-, hydrocarbylmetalloid-, and/orhalohydrocarbylmetalloid-substituted derivative thereof. Cp typicallycontains up to 75 non-hydrogen atoms. B, if present, is typically asilylene (—SiR₂—), benzo (C₆H₄<), substituted benzo, methylene (—CH₂—),substituted methylene, ethylene (—CH₂CH₂—), or substituted ethylenebridge. M is preferably a metal atom of Groups 4-6, and most preferablyis a Group 4 metal atom, especially hafnium, and most especiallyzirconium. L can be a divalent substituent such as an alkylidene group,a cyclometallated hydrocarbyl group, or any other divalent chelatingligand, two loci of which are singly bonded to M to form a cyclic moietywhich includes M as a member. In most cases L is methyl. X, if present,can be a leaving group or a non-leaving group, and thus can be a halogenatom, a hydrocarbyl group (alkyl, cycloalkyl, alkenyl, cycloalkenyl,aryl, aralkyl, etc.), hydrocarbyloxy, (alkoxy, aryloxy, etc.) siloxy,amino or substituted amino, hydride, acyloxy, triflate, and similarunivalent groups that form stable metallocenes. The sum of b, c, and dis a whole number, and is often from 3-5. When M is a Group 4 metal oran actinide metal, and b is 2, the sum of c and d is 2, c being atleast 1. When M is a Group 3 or Lanthanide metal, and b is 2, c is 1 andd is zero. When M is a Group 5 metal, and b is 2, the sum of c and d is3, c being at least 2.

Also incorporated in this invention are compounds analogous to those ofFormula I where one or more of the Cp groups are replaced by cyclicunsaturated charged groups isoelectronic with Cp, such as borabenzene orsubstituted borabenzene, azaborole or substituted azaborole, and variousother isoelectronic Cp analogs. See for example Krishnamurti, et al.,U.S. Pat. No. 5,554,775 and 5,756,611.

In one preferred group of metallocenes, b is 2, i.e., there are twocyclopentadienyl-moiety containing groups in the molecule, and these twogroups can be the same or they can be different from each other.

Another sub-group of useful metallocenes which can be used in thepractice of this invention are metallocenes of the type described in WO98/32776 published Jul. 30, 1998. These metallocenes are characterizedin that one or more cyclopentadienyl groups in the metallocene aresubstituted by one or more polyatomic groups attached via a N, O, S, orP atom or by a carbon-to-carbon double bond. Examples of suchsubstituents on the cyclopentadienyl ring include —OR, —SR, —NR2, —CH═,—CR═, and —PR₂, where R can be the same or different and is asubstituted or unsubstituted C₁-C₁₆ hydrocarbyl group, a tri-C₁-C₈hydrocarbylsilyl group, a tri-C₁-C₈ hydrocarbyloxysilyl group, a mixedC₁-C₈ hydrocarbyl and C₁-C₈ hydrocarbyloxysilyl group, a tri-C₁-C₈hydrocarbylgermyl group, a tri-C₁-C₈ hydrocarbyloxygermyl group, or amixed C₁-C₈ hydrocarbyl and C₁-C₈ hydrocarbyloxygermyl group.

Examples of metallocenes to which this invention is applicable includesuch compounds as:

bis(methylcyclopentadienyl)titanium dimethyl;

bis(methylcyclopentadienyl)zirconium dimethyl;

bis(n-butylcyclopentadienyl)zirconium dimethyl;

bis(dimethylcyclopentadienyl)zirconium dimethyl;

bis(diethylcyclopentadienyl)zirconium dimethyl;

bis(methyl-n-butylcyclopentadienyl)zirconium dimethyl;

bis(n-propylcyclopentadienyl)zirconium dimethyl;

bis(2-propylcyclopentadienyl)zirconium dimethyl;

bis(methylethylcyclopentadienyl)zirconium dimethyl;

bis(indenyl)zirconium dimethyl;

bis(methylindenyl)zirconium dimethyl;

dimethylsilylenebis(indenyl)zirconium dimethyl;

dimethylsilylenebis(2-methylindenyl)zirconium dimethyl;

dimethylsilylenebis(2-ethylindenyl)zirconium dimethyl;

dimethylsilylenebis(2-methyl-4-phenylindenyl)zirconium dimethyl;

1,2-ethylenebis(indenyl)zirconium dimethyl;

1,2-ethylene bis(methylindenyl)zirconium dimethyl;

2,2-propylidenebis(cyclopentadienyl)(fluorenyl)zirconium dimethyl;

dimethylsilylenebis(6-phenylindenyl)zirconium dimethyl;

bis(methylindenyl)zirconium benzyl methyl;

ethylenebis[2-(tert-butyldimethylsiloxy)-1-indenyl]zirconium dimethyl;

dimethylsilylenebis(indenyl)chlorozirconium methyl;

5-(cyclopentadienyl)-5-(9-fluorenyl)1-hexene zirconium dimethyl;

dimethylsilylenebis(2-methylindenyl)hafnium dimethyl;

dimethylsilylenebis(2-ethylindenyl)hafnium dimethyl;

dimethylsilylenebis(2-methyl-4-phenylindenyl)hafnium dimethyl;

2,2-propylidenebis(cyclopentadienyl)(fluorenyl)hafnium dimethyl;

bis(9-fluorenyl)(methyl)(vinyl)silane zirconium dimethyl;

bis(9-fluorenyl)(methyl)(prop-2-enyl)silane zirconium dimethyl;

bis(9-fluorenyl)(methyl)(but-3-enyl)silane zirconium dimethyl;

bis(9-fluorenyl)(methyl)(hex-5-enyl)silane zirconium dimethyl;

bis(9-fluorenyl)(methyl)(oct-7-enyl)silane zirconium dimethyl;

(cyclopentadienyl)(1-allylindenyl)zirconium dimethyl;

bis(1-allylindenyl)zirconium dimethyl;

(9-(prop-2-enyl)fluorenyl)(cyclopentadienyl)zirconium dimethyl;

(9-(prop-2-enyl)fluorenyl)(pentamethylcyclopentadienyl)zirconiumdimethyl;

bis(9-(prop-2-enyl)fluorenyl)zirconium dimethyl;

(9-(cyclopent-2-enyl)fluorenyl)(cyclopentadienyl)zirconium dimethyl;

bis(9-(cyclopent-2-enyl)(fluorenyl)zirconium dimethyl;

5-(2-methylcyclopentadienyl)-5(9-fluorenyl)-1-hexene zirconium dimethyl;

1-(9-fluorenyl) 1-(cyclopentadienyl)-1-(but-3-enyl)-1-(methyl)methanezirconium dimethyl;

5-(fluorenyl)-5-(cyclopentadienyl)-1-hexene hafnium dimethyl;

(9-fluorenyl)(1-allylindenyl)dimethylsilane zirconium dimethyl;

1-(2,7-di(alpha-methylvinyl)(9-fluorenyl)-1-(cyclopentadienyl)-1,1-dimethylmethanezirconium dimethyl;

1-(2,7-di(cyclohex-1-enyl)(9-fluorenyl))-1-(cyclopentadienyl)-1,1-methanezirconium dimethyl;

5-(cyclopentadienyl)-59-fluorenyl)-1-hexene titanium dimethyl;

5-(cyclopentadienyl)-5-(9-fluorenyl)1-hexene titanium dimethyl;

bis(9-fluorenyl)(methyl)(vinyl)silane titanium dimethyl;

bis(9-fluorenyl)(methyl)(prop-2-enyl)silane titanium dimethyl;

bis(9-fluorenyl)(methyl)(but-3-enyl)silane titanium dimethyl;

bis(9-fluorenyl)(methyl)(hex-5-enyl)silane titanium dimethyl;

bis(9-fluorenyl)(methyl)(oct-7-enyl)silane titanium dimethyl;

(cyclopentadienyl)(1-allylindenyl) titanium dimethyl;

bis(1-allylindenyl)titanium dimethyl;

(9-(prop-2-enyl)fluorenyl)(cyclopentadienyl)hafnium dimethyl;

(9-(prop-2-enyl)fluorenyl)(pentamethylcyclopentadienyl)hafnium dimethyl;

bis(9-(prop-2-enyl)fluorenyl)hafnium dimethyl;

(9-(cyclopent-2-enyl)fluorenyl)(cyclopentadienyl)hafnium dimethyl;

bis(9-(cyclopent-2-enyl)(fluorenyl)hafnium dimethyl;

5-(2-methylcyclopentadienyl)-5(9-fluorenyl)-1-hexene hafnium dimethyl;

5-(fluorenyl)-5-(cyclopentadienyl)-1-octene hafnium dimethyl;

(9-fluorenyl)(1-allylindenyl)dimethylsilane hafnium dimethyl;

(tert-butylamido)dimethyl(tetramethylcyclopentadienyl)silanetitanium(1,3-pentadiene);

(cyclopentadienyl)(9-fluorenyl)diphenylmethane zirconium dimethyl;

(cyclopentadienyl)(9-fluorenyl)diphenylmethane hafnium dimethyl;

dimethylsilanylene-bis(indenyl)thorium dimethyl;

dimethylsilanylene-bis(4,7-dimethyl-1-indenyl)zirconium dimethyl;

dimethylsilanylene-bis(indenyl)uranium dimethyl;

dimethylsilanylene-bis(2-methyl-4-ethyl-1-indenyl)zirconium dimethyl;

dimethylsilanylene-bis(2-methyl-4,5,6,7-tetrahydro-1-indenyl)zirconiumdimethyl;

(tert-butylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanetitanium dimethyl;

(tert-butylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanechromium dimethyl;

(tert-butylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanetitanium dimethyl;

(phenylphosphido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanetitanium dimethyl; and

[dimethylsilanediylbis(indenyl)]scandium methyl.

In many cases the metallocenes such as referred to above will exist asracemic mixtures, but pure enantiomeric forms or mixtures enriched in agiven enantiomeric form can be used.

A feature of this invention is that not all metallocenes can producecompositions having the excellent catalytic activity possessed by thecompositions of this invention. For example, in the absence of aseparate metal alkyl compound, bis(cyclopentadienyl)dichlorides of Zrcannot produce the compositions of this invention because the chlorideatoms are not capable of serving as leaving groups under the conditionsused in forming the compositions of this invention. Thus on the basis ofthe state of present knowledge, in order to practice this invention, itis desirable to perform preliminary tests with any given previouslyuntested metallocene to determine catalytic activity of the product ofreaction with a hydroxyaluminoxane. In conducting such preliminarytests, use of the procedures and reaction conditions of the Examplespresented hereinafter, or suitable adaptations thereof, is recommended.

In another embodiment of this invention, contrary to that which waspreviously known, it now surprisingly has been found that rac-ethylenebis(1-indenyl)zirconium dimethyl also can be used to produce apolymerization catalyst composition of this invention which exhibitscatalytic activity. Example 15 hereinafter illustrates the preparationand use of this catalyst composition as an olefin polymerizationcatalyst.

Reaction Conditions

To produce the catalytically active catalyst compositions of thisinvention the reactants, the d- or f-block metal compound, and thehydroxyaluminoxane that has either been freshly prepared or stored atlow temperature (e.g., −10° C. or below) are brought together preferablyin solution form or on a support. The reaction between the hydroxy groupand the bond between the leaving group and the d- or f-block metal isstoichiometric and thus the proportions used should be approximatelyequimolar. The temperature of the reaction mixture is kept in the rangeof about −78 to about 160° C. and preferably in the range of about 15 toabout 30° C. The reaction is conducted under an inert atmosphere and inan inert environment such as in an anhydrous solvent medium. Reactiontimes are short, typically within four hours. When the catalystcomposition is to be in supported form on a catalyst support or carrier,the suitably dried, essentially hydrate-free support can be included inthe reaction mixture. However, it is possible to add the catalyst to thesupport after the catalyst composition has been formed.

When substituting for the hydroxyaluminoxane reactant in thesereactions, a composition in the form of one or more individual solidsformed from a hydroxyaluminoxane and a carrier material, the reactionconditions for producing the active catalyst compositions will be thesame as those taught in the preceding paragraph, with the additionalnote that use of such composition suspended in a viscous inert liquid(e.g., mineral oil) as previously discussed herein may be preferred incertain applications as the source of the hydroxyaluminoxane reactant.The presence of such viscous inert liquid can act to insulate theresulting activated catalyst composition from air or other reactants inthe surrounding environment, and can otherwise facilitate handling ofthe catalyst compositions. The use of the co-catalyst compositions ofmatter on carrier material in forming the active catalyst compositionare preferred over unsupported hydroxyaluminoxane, since it provides amore fin stable reactant (the hydroxyaluminoxane/carrier composition) interms of OH-decay as compared to unsupported hydroxyaluminoxane, whichin turn enables the use of lower amounts (on a molar basis) of thehydroxyaluminoxane/carrier composition to obtain at least the same levelof activation.

It should also be noted that, just as in the formation of theco-catalyst compositions from hydroxyaluminoxane and a carrier material,the catalysts may be formed by bringing together the metal compound andthe co-catalyst without isolating the co-catalyst from solution. Thus,for example, the metal compound may be mixed with the co-catalystcomposition in the same reaction vessel or zone in which the co-catalystcomposition is formed, and whether the co-catalyst is formed by bringingtogether a starting hydroxyaluminoxane and a carrier material, or bybringing together a starting aluminium alkyl, a carrier material in aninert solvent, and water under co-catalyst forming conditions. In otherwords, the metal compound may be brought together with a mixture inwhich the co-catalyst may be formed in order to form the activatedcatalyst composition in situ, whereupon the catalyst composition may beisolated and used or stored for later use as a polymerization catalyst.The reaction conditions for in situ formation of the active catalystcompositions should be the same as those taught above generally for theformation of the active catalyst compositions. Accordingly, anotherembodiment of this invention is the process which comprises bringingtogether, in an inert solvent, an aluminum alkyl and a carrier materialto form a first mixture, bringing together the first mixture and a watersource to form a second mixture in which a supported hydroxyaluminoxaneis formed, and then bringing the second mixture together with the d- orf-block metal compound to form a third mixture in which an activatedpolymerization catalyst on support is formed. If desired, the activatedcatalyst then may be isolated from the third mixture. This embodimentpresents a particularly economical way of producing the desired catalystin a supported and highly stable form.

Recovery of the Active Catalyst Compositions

Typically the active catalyst composition can be recovered from thereaction mixture in which it was formed simply by use of a knownphysical separation procedure. Since the reaction involved in theformation of the product preferably uses a metallocene having one or twomethyl groups whereby gaseous methane is formed as the coproduct, themetal-containing catalyst product is usually in a reaction mixturecomposed almost entirely of the desired catalyst composition and thesolvent used. This renders the recovery procedure quite facile. Forexample, where the product is in solution in the reaction mixture, thesolvent can be removed by stripping off the solvent under reducedpressure and at moderately elevated temperature. Often the residualproduct recovered in this manner is of sufficient purity that furtherpurification is not required. In the event the product is in the form ofsolids which precipitate from the solvent, or which are caused toprecipitate from the solution by the addition of a suitable non-solvent,physical solid-liquid separation procedures such as filtration,centrifugation, and/or decantation can be employed. The productrecovered in this manner is usually of sufficient purity that furtherpurification is not required. Whatever the method of recovery used, iffurther purification is needed or desired, conventional purificationsteps, such as crystallization can be used.

The product need not be recovered or isolated directly from the liquidreaction medium in which it was prepared. Instead, it can be transferredto another solvent, for example, by use of a solvent extractionprocedure or a solvent swap procedure whereby the product is removedfrom the liquid phase in which it was produced and is thus dissolved ina different solvent. Although unnecessary, this new solution can besubjected to still another solvent extraction, or solvent swap, as manytimes as desired, recognizing of course that the longer the productremains in solution the greater the opportunity for product degradationto occur. In any case referred to in this paragraph, the catalyticallyactive product is recovered or isolated from a solution other than theliquid phase in which it was produced, and is maintained in undissolvedcondition under dry, anhydrous conditions.

Storage of Recovered Active Catalyst Compositions

The recovered catalyst compositions of this invention can be stored inany suitable air-tight container either under vacuum or under anatmosphere of anhydrous inert gas, such as nitrogen, helium, argon, orthe like. To protect against possible light-induced degradation, thecontainer is preferably opaque or rendered opaque toward lighttransmission and/or the package containing the catalyst composition iskept in a suitable dark storage area. Likewise it is desirable to storethe product in locations that will not become excessively hot. Exposureto storage temperatures of up to about 30° C. typically will cause nomaterial loss in activity, but naturally the effect of temperatureslikely to be encountered during storage should be determined for anygiven catalyst where such information has not previously beenascertained.

The length of time during which the recovered active catalystcomposition is stored can be as short as a minute or less. For example,the active catalyst composition could be produced in an appropriateamount at the site of the polymerization and immediately upon isolationcould be directly transferred to the polymerization reaction vessel. Thestorage period in such case could be very short, namely the time betweenisolation of the active catalyst composition and commencement of its useas the catalyst in the polymerization. On the other hand, the storageperiod can be substantially longer provided that the storage occursunder the appropriate conditions at all times during the storage. Forexample, the active catalyst composition could be produced, placed in asuitable air-tight, moisture-resistant vessel or container under a dry,anhydrous atmosphere promptly after its isolation, and then maintainedin inventory in a suitable air-tight, moisture-resistant vessel orcontainer under a dry, anhydrous atmosphere, all at the site of itsmanufacture, and with these steps being conducted such that the amountof exposure to air or moisture, if any, is kept at all times to such aminimal amount as not to adversely affect the activity of the catalystcomposition. All or a portion of such stored active catalyst compositioncould then be shipped under these same conditions to another site,typically the site where its use as a polymerization catalyst is to takeplace. And after reaching the site where the composition is to be usedas a catalyst, the composition could then again be kept in inventoryunder the same or substantially the same type of suitable storageconditions at that site until portions of the catalyst composition areput to use as a catalyst. In such a case the overall storage periodcould be very long, e.g. as long as the particular catalyst compositionretains suitable catalytic activity. Thus the period of storage isdiscretionary and is subject to no numerical limitation as it can dependon such factors as the extent of care exercised in the various steps towhich the stored product is subjected during storage, the conditionsexisting or occurring during the storage, and so on. Thus as a practicalmatter the period of time of the storage can be the period of timeduring which the catalyst does not lose its activity or effectivenesswhen used as a polymerization catalyst.

The catalyst compositions of this invention can be stored in isolatedform, or in various other undissolved forms. For example, afterrecovery, the active catalyst composition can be mixed under dry,anhydrous conditions with dry inert materials such as calcinedparticulate or powdery silica, alumina, silica-alumina, clay,montmorillonite, diatomaceous earth, or like substance, and theresultant dry blend can be stored under appropriate dry, anhydrousconditions. Similarly, after recovery, the active catalyst compositioncan be mixed under dry, anhydrous conditions with other kinds of dryinert materials such as chopped glass fibers, glass beads, carbonfibers, metal whiskers, metal powders, and/or other materials commonlyused as reinforcing fillers for polymers, and the resultant blends canthen be stored under appropriate dry, anhydrous conditions. In apreferred embodiment, after recovery, the active catalyst composition issupported on a dry catalyst support material such as calcined silica,calcined silica-alumina, calcined alumina, particulate polyethylene,particulate polypropylene, or other polyolefin homopolymer or copolymerunder anhydrous air-free conditions using known technology, and theresultant supported catalyst composition is then stored underappropriate dry, anhydrous conditions. In case anyone needs to be toldwhat “appropriate conditions” are, they include not exposing the storedcatalyst composition to such high temperatures as would causedestruction of the catalyst or its catalytic activity, and not exposingthe stored catalyst to light wave energy or other forms of radiation ofsuch type or magnitude as would cause destruction of the catalyst or itscatalytic activity. Here again, this disclosure as any patentdisclosure, should be read with at least a little common sense, ratherthan with legalistic word play in mind.

The catalyst compositions of this invention are particularly stable, asthey typically will be able to be maintained in a dry state underanhydrous or substantially anhydrous conditions and at a temperature inthe range of about 5 to about 70° C., more preferably in the range ofabout 10 to about 60° C., and most preferably in the range of about 15to about 35° C., for a period of time of at least about 24 hours, morepreferably for at least about 48 hours, and most preferably at leastabout 72 hours, without losing fifty percent (50%) or more of itscatalytic activity. It should be appreciated that such catalyticactivity would be measured in terms of grams of polymer per gram ofcatalyst composition per hour, samples being compared using identicalpolymerization reaction conditions.

Polymerization Processes Using Catalysts of this Invention

The catalyst compositions of this invention can be used in solution ordeposited on a solid support. Depositing upon a carrier or solid supportis particularly preferred. When used in solution polymerization, thesolvent can be, where applicable, a large excess quantity of the liquidolefinic monomer. Typically, however, an ancillary inert solvent,typically a liquid paraffinic or aromatic hydrocarbon solvent is used,such as heptane, isooctane, decane, toluene, xylene, ethylbenzene,mesitylene, or mixtures of liquid paraffinic hydrocarbons and/or liquidaromatic hydrocarbons. When the catalyst compositions of this inventionare supported on a carrier, the solid support or carrier can be anysuitable particulate solid, and particularly a porous support such astalc, zeolites, or inorganic oxides, or resinous support material suchas polyolefins. Preferably, the support material is an inorganic oxidein finely divided form.

Suitable inorganic oxide support materials which are desirably employedinclude metal oxides such as silica, alumina, silica-alumina andmixtures thereof. Other inorganic oxides that may be employed eitheralone or in combination with the silica, alumina or silica-alumina aremagnesia, titania, zirconia, and like metal oxides. Other suitablesupport materials are finely divided polyolefins such as finely dividedpolyethylene.

Polymers can be produced pursuant to this invention byhomopolymerization of polymerizable olefins, typically 1-olefins (alsoknown as α-olefins) such as ethylene, propylene, 1-butene, orcopolymerization of two or more copolymerizable monomers, at least oneof which is typically a 1-olefin. The other monomer(s) used in formingsuch copolymers can be one or more different 1-olefins and/or adiolefin, and/or a polymerizable acetylenic monomer. Olefins that can bepolymerized in the presence of the catalysts of this invention includeα-olefins having 2 to 20 carbon atoms such as ethylene, propylene,1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene,1-tetradecene, 1-hexadecene, and 1-octadecene. Other suitable monomersfor producing homopolymers and copolymers include styrenic monomers,e.g., styrene, ar-methylstyrenes, alpha-methylstyrene,ar-dimethylstyrenes, ar-ethylstyrene, 4-tert-butylstyrene, andvinylnaphthalene. Still other suitable monomers include polycyclicmonomers. Illustrative examples of suitable polycyclic monomers include2-norbornene, 5-methyl-2-norbornene, 5-hexyl-2-norbornene,5-decyl-2-norbornene, 5-phenyl-2-norbornene, 5-naphthyl-2-norbornene,5-ethylidene-2-norbornene, vinylnorbornene, dicyclopentadiene,dihydrodicyclopentadiene, tetracyclododecene, methyltetracyclododecene,tetracyclododecadiene, dimethyltetracyclododecene,ethyltetracyclododecene, ethylidenyl tetracyclododecene,phenyltetracyclododecene, trimers of cyclopentadiene (e.g., symmetricaland asymmetrical trimers). Copolymers based on use of isobutylene as oneof the monomers can also be prepared. Normally, the hydrocarbon monomersused, such as 1-olefins, diolefins and/or acetylene monomers, willcontain up to about 10 carbon atoms per molecule. Preferred 1-olefinmonomers for use in the process include ethylene, propylene, 1-butene,3-methyl-1-butene, 4-methyl-1-pentene, 1-hexene, and 1-octene. It isparticularly preferred to use supported catalysts of this invention inthe polymerization of ethylene, or propylene, or ethylene and at leastone C₃-C₈ 1-olefin copolymerizable with ethylene. Typical diolefinmonomers which can be used to form terpolymers with ethylene andpropylene include butadiene, hexadiene, norbornadiene, and similarcopolymerizable diene hydrocarbons. 1-Heptyne and 1-octyne areillustrative of suitable acetylenic monomers which can be used.

Polymerization of ethylene or copolymerization with ethylene and anα-olefin having 3 to 10 carbon atoms may be performed in either the gasor liquid phase (e.g. in a diluent, such as toluene, or heptane). Thepolymerization can be conducted at conventional temperatures (e.g., 0°to 120° C.) and pressures (e.g., ambient to 50 kg/cm²) usingconventional procedures as to molecular weight regulations and the like.

The heterogeneous catalysts of this invention can be used inpolymerizations conducted as slurry processes or as gas phase processes.By “slurry” is meant that the particulate catalyst is used as a slurryor dispersion in a suitable liquid reaction medium which may be composedof one or more ancillary solvents (e.g., liquid aromatic hydrocarbons,etc.) or an excess amount of liquid monomer to be polymerized in bulk.Generally speaking, these polymerizations are conducted at one or moretemperatures in the range of about 0 to about 160° C., and underatmospheric, subatmospheric, or superatmospheric conditions.Conventional polymerization adjuvants, such as hydrogen, may be employedif desired. Preferably polymerizations conducted in a liquid reactionmedium containing a slurry or dispersion of a catalyst of this inventionare conducted at temperatures in the range of about 40 to about 110° C.Typical liquid diluents for such processes include hexane, toluene, andlike materials. Typically, when conducting gas phase polymerizations,superatmospheric pressures are used, and the reactions are conducted attemperatures in the range of about 50 to about 160° C. These gas phasepolymerizations can be performed in a stirred or fluidized bed ofcatalyst in a pressure vessel adapted to permit the separation ofproduct particles from unreacted gases. Thermostated ethylene,comonomer, hydrogen and an inert diluent gas such as nitrogen can beintroduced or recirculated to maintain the particles at the desiredpolymerization reaction temperature. An aluminum alkyl such astriethylaluminum may be added as a scavenger of water, oxygen and otherimpurities. In such cases the aluminum alkyl is preferably employed as asolution in a suitable dry liquid hydrocarbon solvent such as toluene orxylene. Concentrations of such solutions in the range of about 5×10⁻⁵molar are conveniently used. But solutions of greater or lesserconcentrations can be used, if desired. Polymer product can be withdrawncontinuously or semi-continuously at a rate that maintains a constantproduct inventory in the reactor.

The catalyst compositions of this invention can also be used along withsmall amounts of hydrocarbylborane compounds such as triethylborane,tripropylborane, tributylborane, tri-sec-butylborane. When so used,molar Al/B ratios in the range of about 1/1 to about 1/500 can be used.

Because of the high activity and productivity of the catalysts of thisinvention, the catalyst levels used in olefin polymerizations can beless than previously used in typical olefin polymerizations conducted onan equivalent scale. In general, the polymerizations andcopolymerizations conducted pursuant to this invention are carried outusing a catalytically effective amount of a novel catalyst compositionof this invention, which amount may be varied depending upon suchfactors such as the type of polymerization being conducted, thepolymerization conditions being used, and the type of reaction equipmentin which the polymerization is being conducted. In many cases, theamount of the catalyst of this invention used will be such as to providein the range of about 0.000001 to about 0.01 percent by weight of d- orf-block metal based on the weight of the monomer(s) being polymerized.

After polymerization the product polymer can be recovered from thepolymer by any suitable means. When conducting the process in slurry,dispersion or bulk monomer (e.g. liquid propylene) media the product istypically recovered and dried by a physical separation technique using adevice such as a wiped film evaporator (WFE) or similar distillativetechniques. Alternatively the polymer can be separated by filtration ordecantation methods. When conducting the process as a gas phasepolymerization the resulting polymer is freed from residual monomer byany suitable means such as purging with nitrogen, with or withoutadditional heating. When the catalysts are employed in solutionpolymerization processes the product is again recovered and dried by anysuitable physical separation technique, usually involving evaporation.Alternatively the polymer can be precipitated from solution by adding asuitable non-solvent (e.g. heptane, iso-propanol, acetone) and thenrecovered by any suitable physical separation technique followed bydrying.

Due to the high productivity of the catalysts it is not usuallynecessary to deactivate the catalyst nor to extract catalyst residuesprior to recovering the product polymer. However if desired the catalystcan be deactivated in the conventional manner by applying a short-stopsuch as an alcohol (e.g. iso-propanol), oxygen, carbon monoxide, carbondioxide or water or mixtures thereof. Furthermore, if required thecatalyst residues and other impurities (such as less volatile monomers)can be removed by washing with one or more suitably volatile solventssuch as iso-propanol, iso-butanol, acetone, methylethylketone, aliphaticor aromatic hydrocarbons.

When preparing polymers pursuant to this invention conditions may beused for preparing unimodal or multimodal polymer types. For example,mixtures of catalysts of this invention formed from two or moredifferent metallocenes having different propagation and termination rateconstants for ethylene polymerizations can be used in preparing polymershaving broad molecular weight distributions of the multimodal type.

Experimental Section

The following Examples are presented for purposes of illustration andnot limitation. All operations of these Examples were carried out undernitrogen either in a drybox with below 1 ppm oxygen or using standardSchlenk line techniques. Methylaluminoxane (MAO), triisobutylaluminum(TIBA), triethylaluminum (TEA), were commercial products of AlbemarleCorporation and used as received. Reagents benzylmagnesium chloride andMeLi with LiBr were purchased from Aldrich and used as received.Toluene, ethylene, propylene, and nitrogen used in the polymerizationreactions were purified by passing through a series of three cylinders:molecular sieves, Oxyclear oxygen absorbent, and alumina. Ethylene andpropylene were polymer grade from Matheson. Toluene for catalystpreparation and spectros- copy studies was Aldrich anhydrous grade andwas distilled from sodium/benzophenone ketyl. Hexane was Aldrichanhydrous grade and stored over Na/K alloy. The metallocenes used inthese Examples were prepared according to procedures given in theliterature. Thus Cp₂ZrMe₂ was prepared using the method of Samuel, etal., J. Am. Chem. Soc., 1973, 95, 6263;rac-dimethylsilylbis(2-methyl-1-indenyl)zirconium dichloride using themethod of Spaleck, et al., Angew. Chem., Int. Ed. Engl., 1992, L, 1347,and Winter, et al. U.S. Pat. No. 5,145,819; andbis(1-methyl-3-n-butyl-cyclopentadienyl)zirconium dichloride using themethod of Lee, et al., Canadian Pat. No. 2,164,914, July 1996. TheFT-infrared spectra of FIGS. 1, 2 and 3 were recorded on a NicoletMagna-IR 750 spectrometer with 32 scans and 2 cm⁻¹ resolution using 0.5mm NaCl cells. The absorption of hexane was compensated by subtractionwith a reference hexane spectrum acquired from the same cell. The UV-Visspectra were recorded in the 290-700 nm region on a Varian Cary 3Espectrometer. Quartz cuvettes of 1 cm pathlength were used. Diffusereflectance infrared fourier transform spectroscopy (DRIFTS) use aNicolet Magna 750 FTIR bench equipped with a “Collector” diffusereflectance accessory from spectra-Tech with a high temperature/highpressure sample chamber. The DRIFTS spectra (FIG. 8) were obtained at 4cm−1 resolution and 128 scans. The molecular weight and molecular weightdistribution were determined by gel permeation chromatography whichincorporated three different modes of detection including differentialrefractive index (Polymer Labs), laser light scattering (PrecisionDetectors) and differential pressure viscometry (Viscotek Corporation).The chromatographic instrument was a Polymer Labs 210 using1,2,4-trichlorobenezene as the eluting solvent at 150° C. A series oflinear mixed bed GPC columns were used to perform the separation and thedata was collected and analyzed using Viscotek's TriSEC softwarepackage. The samples were dissolved in the tricholorbenzene for 2-4hours at 150° C. at a concentration of approximately 2000 rpm.MFI, meltflow index, was determined by the ASTM D1238 method.

EXAMPLE 1 Rac-dimethylsilylbis(2-methylindenyl)zirconium dimethyl(MET-A)

Rac-dimethylsilylbis(2-methylindenyl)zirconium dichloride (5.03 g, 10.55mmol) was suspended in 100 g of toluene. The orange slurry was heated inan oil bath to 40° C. Most of the orange-yellow metallocene remainedundissolved. MeLi/LiBr (5.87 wt % in ether, 7.78 g) was added dropwiseover two hours. The solution became amber/yellow and the solidslightened. The reaction was allowed to cool to ambient temperature andstir overnight. Analysis of the reaction showed 9.3 mol % of mono-methylintermediates. Additional aliquots of MeLi/LiBr (1.66 g) were addeddropwise until the monomethyl intermediates were reduced to less thantwo mol %. Approximately a quarter of the solvent was removed in vacuoand then the lithium salts were filtered on a medium frit and washedwith 20 mL of toluene. The combined filtrates were concentrated invacuo. A yellow crystalline solid formed. The slurry was cooled to −20°C. The yellow crystals were filtered on a coarse frit. After drying invacuo, the yield of rac-dimethylsilyl-bis(2-methylindenyl)zirconiumdimethyl was 3.20 g (70%).

EXAMPLE 2 Bis(1-butyl-3-methylcyclopentadienyl)zirconium dimethyl(MET-B)

Bis(1-butyl-3-methylcyclopentadienyl)zirconium dichloride (2.71 g, 6.26mmol) was dissolved in 21.4 g of toluene. Low-halide MeLi (˜0.5 M inether, 8.0 mL) was added dropwise at ambient temperature. A white solidformed immediately. The reaction was allowed to stir for 1.5 hours.Analysis of the reaction showed 3.5 mol % of mono-methyl intermediate.An additional aliquot of MeLi (0.4 mL) was then added to consume themonomethyl intermediate. After stirring overnight, the supernatantliquid was reanalyzed to verify that the reaction was complete. Theslurry was filtered on a medium frit and the solvent was removed invacuo. A light yellow liquid ofbis(1-butyl-3-methyl-cyclopentadienyl)-zirconium dimethyl remained (2.13g, 87% yield).

EXAMPLE 3 Synthesis of Hydroxyisobutylaluminoxane (HO-IBAO)

The reaction was carried out in a 1-L, three-necked, round-bottomedMorton flask equipped with a thermometer, an outlet connected to aSchlenk line, and a rubber septum through which water was added via asyringe needle. To this flask containing a solution oftriisobutylaluminum (98.4 g, 492.4 mmol) in hexane (276.4 g) withvigorous magnetic stirring was added degassed water (8.85 g, 491.4 mmol)using a syringe pump over a period of 65 minutes. The temperature wasmaintained at between −5 and 0° C. by applying a dry ice bath (withoutacetone) and by adjusting water addition speed. After the water additionwas complete, the solution was stirred for an additional ten minutes (oruntil the exothermic reaction subsided, which usually lasts about 5-10minutes after completion of water addition), stripped of dissolvedisobutane and some hexane under vacuum at a temperature somewhat belowambient, transferred, and stored in a −10° C. freezer in a drybox. Thesolution weighed 252.2 g and was determined by analysis to have a wt %Al of 5.15.

EXAMPLE 4 Synthesis of Deuteroxyisobutylaluminoxane (DO-IBAO)

The procedure of Example 3 was repeated with the exception that anequivalent amount of D₂O was used in place of the water and theoperation was conducted with similar amounts of the reactants.

EXAMPLE 5 Characterization of HO-IBAO by IR-Spectroscopy

The presence of hydroxyl groups in the product solution of Example 3 wasindicated by an infrared spectrum (see FIG. 1) taken the next day.Initially, there are two types of hydroxyl groups detected at 3615 cm⁻¹(major) and 3695 cm⁻¹ (minor), respectively. At room temperature, bothare unstable particularly the major one. The stability study was carriedout with another reaction solution in hexane (Al wt %=3.55,H₂O/Al=1.00). The liquid cuvette was left in the IR chamber at ambienttemperature and spectra were recorded at the indicated intervals (seeFIG. 2). The last spectrum taken after two days at ambient temperature,revealed possibly two additional OH frequencies at 3597 cm⁻¹ and 3533cm⁻¹. The stability of the hydroxyls groups depends on a number offactors. For instance, the hydroxyl groups can be preserved for a muchlonger time if the solution is kept at a lower temperature, or if addedtetrahydrofuran which stabilizes the hydroxyls both by forminghydrogen-bonds, and by coordinating to aluminum sites; or by using ahigher hydrolysis ratio (hydroxyls are more stable in IBAO ofwater/Al=1.00 than in IBAO of water/Al=0.90).

As indicated by Example 4, the hydroxyl groups can be replaced bydeuteroxy groups by hydrolyzing TIBA with D₂O. A new IR band assignableto OD stretching appeared at 2665 cm⁻¹ corresponding to the 3615 cm⁻¹band for OH stretching (the corresponding OD band for the 3695 cm⁻¹stretching is not seen, presumably obscured by large C—H bands nearby).The ratio of two frequencies (n_(OH)/n_(OD)=1.356) indicates that thisOH or OD group is free or not engaged in any intra or intermolecularhydrogen bonding (the theoretical value is 1.35 which fallssystematically as the strengths of the hydrogen bond increases; see L.J. Bellamy, The Infrared Spectra of Complex Molecules, Volume Two,Second Edition, 1980, page 244, Chapman and Hall). Deuterated isobutane,(CH₃)₂CHCH₂D, a by-product of the hydrolysis reaction, was also detectedby IR as two equally intense bands at 2179 cm⁻¹ and 2171 cm⁻¹,respectively.

To enable correlation between IR absorbance and hydroxy content ofHO-IBAO, a quantitative determination of hydroxy content was performed(Example 6). In the absence of a model compound with known hydroxycontent, IR spectroscopy provides only qualitative information.

EXAMPLE 6 Quantification of Hydroxy Content in HO-IBAO; Benzyl GrignardMethod

To a cold, vigorously stirred HO-IBAO solution (5.52 g solution, 10 mmolAl) with a 4.89 wt % Al and an IR absorbance of 0.557 for the 3616 cm⁻¹band was added a 2-M solution of benzylmagnesium chloride in THF (2.0ml, 4 mmol). The mixture quickly reacted becoming two layers and wasstiffed at ambient temperature for 90 minutes. After that, the resultingsuspension was vacuum distilled at temperatures up to 50° C. over onehour and all volatiles were trapped in a flask cooled by a liquidnitrogen bath. The amount of toluene in the collected liquid wasdetermined by GC (with a known amount of pentadecane added as aninternal reference) to be 0.66 mmol, which corresponds to 6.6 OH groupsfor every 100 Al atoms.

The mechanism as depicted in Equation (2) above was proved by the use oftwo different experiments, one involving deuterium labeling and GC-massspectographic analysis (Examples 7 and 8), and the other infra-redanalysis (Example 7).

EXAMPLE 7 Verification of Novel Metallocene Activation Mechanism;HO-IBAO Functions As a Brønsted Acid

Use of Deuterium-Labeled Reactant (DO-IBAO) with Unbridged Metallocene.Into a 30-mL round-bottomed flask containing a cold solution ofdeuteroxyisobutylaluminoxane (DO-IBAO) (OD stretching at 2665 cm⁻¹,about 5-7 OD for every 100 Al) (3.31 wt % Al, 9.26 g solution, 11.4 mmolAl) prepared by hydrolyzing the TIBA with D₂O a was added solidbis(cyclopentadienyl)zirconium dimethyl (Cp₂ZrMe2) (33 mg, 0.13 mmol).The flask was immediately closed with a gas tight septum to preventescape of any gaseous products. The volume of the solution was ca. 15 mLwhich left about another 15 mL of headspace in the flask. It took about2-3 minutes for the metallocene solids to dissolve completely to give alight yellow solution. After stirring for 85 minutes at ambienttemperature, a gaseous sample withdrawn from the head space of the flaskwas subjected to GC-Mass Spec analysis which showed a composition of 9.1mol % CH₃D and 90.9 mol % N₂. In other words, 1.37 mL of the 15-mLheadspace was CH₃D, which corresponds to 43% of the theoretical amountpredicted by the reaction of Equation (2) above. The amount of CH₃Dremained dissolved in the solution was not determined. (In fact, if thesolution was cooled to −10 to −20° C., CH₃D in the headspace became toolittle to be detectable by GC-Mass Spec).

EXAMPLE 8 Verification of Novel Metallocene Activation Mechanism;HO-IBAO Functions As a Brønsted Acid

Use of Deuterium-Labeled Reactant (DO-IBAO) with Bridged Metallocene.This reaction was carried out analogously to Example 7 above except thatthe reactants were rac-dimethylsilylbis (2-methyl-1-indenyl)zirconiumdimethyl (45 mg, 0.103 mmol) and DO-IBAO (12.23 g, 15.0 mmol Al) and theflask contained about 19-mL of solution and 11-mL of headspace. TheGC-Mass Spec analysis showed a 4.8 mol % of CH₃D in the headspace, whichcorresponds to 21% of the theoretical amount. The lower percentagereflects the fact that the flask had less headspace and more solutionvolume for CH₃D to dissolve in.

EXAMPLE 9 Verification of Novel Metallocene Activation Mechanism;HO-IBAO Functions As a Brønsted Acid

Use of Infra-Red Analysis of Product from HO-IBAO and a Metallocene. Toa cold, freshly prepared HO-IBAO (3.0 mmol Al, IR spectrum shown in FIG.3 top) in hexane was added soliddimethylsilylbis(methylindenyl)zirconium dimethyl (0.1 mmol, Al/Zr=30).After stirring at ambient temperature for 30 minutes, the resulting deepred-brown solution was taken a IR spectrum shown in FIG. 3 bottom.Separately, another portion of the same cold HO-IBAO solution wasallowed to stand at ambient temperature for 30 minutes and its IRspectrum was taken immediately thereafter (shown in FIG. 3 middle). Itis clear from this set of three spectra that the reaction betweenHO-IBAO and the metallocene results in a rapid disappearance of thehydroxyl groups in IBAO, which cannot be accounted for by the slowerself-consumption during the same period.

EXAMPLE 10 UV-Vis Spectra ofrac-dimethylsilylbis(2-methylindenyl)zirconium dimethyl+Hydroxy IBAOWith Varying Al/Zr Ratios

The reaction between hydroxy IBAO and methylated metallocene can bereadily monitored by UV-Vis. It has been reported that theligand-to-metal charge transfer (LMCT) bands undergo a characteristicbathochromic shift (shorter to longer wavelength) upon converting from aneutral metallocene (catalyst precursor) to a metallocenium cation(active catalyst) by an activator (Siedle, et al., Macromol. Symp.,1995, 89, 299; Pieters, et al., Macromol. Rapid Commun., 1995, 16, 463).For rac-dimethylsilylbis(2-methylindenyl)zirconium dimethyl, an LMCTband (see FIG. 4-solid) appearing at 394 nm (λ_(max), 4710 M⁻¹cm⁻¹)serves as a convenient probe to measure the progress of the activationreaction. As shown in FIG. 4-dotted, the more hydroxy IBAO is used, themore the starting metallocene is consumed and the more adsorption isobserved in the longer wavelength region. It is clear from the spectrathat an Al/Zr ratio of 21 is almost enough to activate all of themetallocene.

As reference to FIG. 5 shows, this spectroscopy tool is also useful formeasuring the effectiveness of a metallocene activator. Thus, ahydroxy-depleted isobutylaluminoxane (aged for three months at ambienttemperature, and indicated by IR to contain no detectable amount ofhydroxyl groups), hardly reacted withrac-dimethylsilylbis(2-methylindenyl)zirconium dimethyl even at a higherAl/Zr ratio of 50. See FIG. 5, middle. Although the metallocene reactswith the tetraisobutyldialuminoxane (TIBAO) (formed using a water/Alratio of 0.50 and used at an Al/Zr ratio of 5000), little bathochromicshift occurred, indicating formation of virtually no active catalystformation. See FIG. 5, bottom. This observation of lack of formation ofactive catalyst was confirmed by the polymerization run described inComparative Example G, below:

The following examples (Examples 11-14 and Comparative Examples A-G)illustrate the highly advantageous results achievable using thepolymerization reactions of this invention.

EXAMPLE 11

The hydroxy IBAO used in this run had 6.16.wt % Al and had been storedin a freezer at −10° C. in drybox for six days. The IR spectrum showedan absorbance of 0.458 for the 3623 cm⁻¹ OH band, which correspondsessentially to an average of 4.2 OH groups per 100 Al atoms.

Polymerization of propylene was carried out in a 2-L stainless steeloil-jacketed reactor which had previously been heated to 100° C. undervacuum for one hour. After the reactor was charged with purified toluene(600 mL) and propylene (400 mL), a 2-mL solution of 1% TIBA in hexanewas injected into the reactor and the mixture was stirred at 50° C. for5 minutes. After that polymerization was initiated by injecting acatalyst solution of rac-dimethylsilylbis(2-methylindenyl)zirconiumdimethyl (2 μmol) and hydroxy IBAO (50 μmol, Al/Zr=25) in 3 mL oftoluene which had previously been allowed to stand at ambienttemperature for one hour. The mixture was stirred at 800 rpm. Thetemperature immediately began to rise from 50° C. to peak at 74° C. 9minutes later. No make-up propylene was added. After ten minutes ofreaction, the unreacted propylene was quickly vented to stop thepolymerization. After adding methanol (>1000 mL), filtering, and dryingthe solids under vacuum at 100° C. overnight, 101 g of isotacticpolypropylene was isolated; polymer properties: M.P. (onset of secondmelt): 146.3° C.; Melt Flow Index (MFW) (230° C./5 kg): 40.68 (g/10min); mmmm %: 93.9%; Isotactic Index: 97.3%.

EXAMPLE 12

This polymerization of propylene used an HO-IBAO which was indicated byIR analysis to contain an average of 4.0 OH groups per 100 Al atoms. Thematerials and procedure were as in Example 11 except that an Al/Zr ratioof 50, and more toluene (800 mL) were used. Yield: 127 g; M.P. (onset ofsecond melt): 144.9° C.; MFI (230° C./5 kg): 87.97 (g/10 min); mmmm %:93.1%; Isotactic Index: 97.4%.

EXAMPLE 13

This HO-IBAO used in this polymerization was indicated by IR analysis tocontain and average of 3.2 OH groups per 100 Al atoms. The materials andprocedure were as in Example 11 except that an Al/Zr ratio of 30, andmore toluene (800 mL) were used. Yield: 88.6 g.; M.P. (onset of secondmelt): 146.9° C.; MFI (230° C./5 kg): 56.28 (g/10 min); mmmm %: 93.1%;Isotactic Index: 96.9%; Molecular weight (via GPC): Mw=167,776,Mn=76,772, Mw/Mn=2.19.

COMPARATIVE EXAMPLE A

The procedure of Example 11 was repeated, except that the catalystsolution was rac-dimethylsilylbis(2-methylindenyl)zirconium dimethyl(1.0 μmol) and conventional methylaluminoxane (MAO) (1.0 mmol,Al/Zr=1000) in toluene, and no TIBA was used as scavenger. Compared toExample 11, this propylene polymerization reaction was much lessexothermic, taking a whole hour of reaction for temperature to rise from50° C. to 81° C.; Yield: 146 g; M.P. (onset of second melt): 144.4° C.;MFI (230° C./5 kg): 79.90 (g/10 min); mmmm %: 92.2%; Isotactic Index:96.5%; Molecular weight (via GPC): Mw=197,463, Mn=84,967, Mw/Mn=2.32.

COMPARATIVE EXAMPLE B

This polymerization was carried out in a 300-mL Parr reactor equippedwith an internal cooling coil. The reactor in drybox was charged with acatalyst solution of rac-dimethylsilylbis(2-methylindenyl)zirconiumdimethyl (0.3 μmol) and MAO (1.5 mmol, Al/Zr=5000) in about 150 mL ofdry toluene. The reactor was sealed, transferred, and heated to 68° C.With stirring set at 800 rpm, the polymerization was initiated bypressing in 28 g of liquid propylene. The temperature was maintained at70° C. by applying cooling intermittently. After 10 minutes, thepolymerization was quenched by adding MeOH. Yield: 7.2 g. M.P. (onset ofsecond melt): 145.9° C.

COMPARATIVE EXAMPLE C

The procedure was as in Example 11 except that the catalyst solution wasrac-dimethylsilylbis(2-methylindenyl)zirconium dimethyl (1.0 μmol) andMAO (0.1 mmol, Al/Zr=100) in toluene. No exothermic reaction wasobserved. The reaction after one hour produced only a trace of solidpolymer.

COMPARATIVE EXAMPLE D

This polymerization used TIBAO (tetraisobutylaluminoxane) made byhydrolyzing TIBA with a half equivalent of water (water to aluminumratio=0.5) and the IR spectrum of the product showed no evidence of anyOH group present. The procedure was as in Example 11 except that anAl/Zr ratio of 100 was used. No polymerization activity was observed.

COMPARATIVE EXAMPLE E

This polymerization was carried out in a 300-mL Parr reactor withprocedure analogous to that in Comparative Example D except that theAl/Zr ratio was 5000, reaction temperature was 70° C., and reaction timewas 20 minutes. Only 0.91 g of polymer was isolated.

COMPARATIVE EXAMPLE F

This polymerization used hydroxyisobutylaluminoxane indicated by IRanalysis to contain an average of 5.3 OH groups per 100 Al atoms. Theprocedure was as in Example 11 except that an Al/Zr ratio of 3000 wasused. The polymerization was initially as exothermic as that inExample 1. However, when the temperature reached 63° C. (from 50° C.)after 4 minutes of reaction, the exothermic reaction suddenly ceased andthe temperature quickly reversed its rising trend, returning to 52° C.in the next 6 minutes. The reaction was allowed to continue for anadditional 20 minutes. Yield: 38.6 g. M.P. (onset of second melt):148.0° C.; MFI (230° C./5 kg): 16.67 (g/10 min); mmmm %: 92.6%;Isotactic Index: 96.8%.

COMPARATIVE EXAMPLE G

This polymerization used hydroxyisobutylaluminoxane indicated by IRanalysis to contain an average of 3.8 OH groups per 100 Al atoms. Theprocedure was as in Example 11 except that the metallocene used wasrac-dimethylsilylbis(2-methylindenyl)zirconium dichloride not thedimethyl analog. In addition, an Al/Zr ratio of 50, and more toluene(800 mL) were used. No reaction was observed.

EXAMPLE 14

This ethylene polymerization used hydroxyisobutylaluminoxane made byhydrolyzing TIBA with 0.9 equivalent of water. This HO-IBAO wasindicated by IR analysis to contain an average of 1.5 OH groups per 100Al atoms at the time of use. The procedure was as in Example 11 with thefollowing modifications: The catalyst used was a mixture ofbis(1-butyl-3-methylcyclopentadienyl)zirconium dimethyl (2 μmol) andhydroxyisobutylaluminoxane (200 μmol), and was allowed to stand atambient temperature for one hour before being injected. The reactor wascharged with 900 mL of dry toluene and pressurized with 300 psig ofethylene, which was fed as needed during polymerization to maintain thepressure. Polyethylene Yield: 55.0 g. M.P. (onset of first melt): 131.8°C. The melt flow index (MFI) was too low to be measured. The molecularweight (via GPC) was as follows: Mw=579,652, Mn=243,129, Mw/Mn=2.38.

Examples 15-19 illustrate the preparation, isolation, and storagestability of the isolated catalyst compounds at ambient roomtemperatures. In these Examples, the stability of the catalyst wasmonitored by UV-Vis spectroscopy. In this method, it is assumed that theabsorbance of the bathochromically shifted metallocenium ion correlateswith the catalyst activity; i.e., the higher the absorbance, the morecatalytically active the metallocene. This correlation has been verifiedby Deffieux's research group in three recently published papers: D.Coevoet et al. Macromol. Chem. Phys., 1998, 199, 1451-1457; D. Coevoetet al. Macromol. Chem. Phys., 1998, 199, 1459-1464; and J. N. Pedeutouret al. Macromol. Chem. Phys., 1999, 199, 1215-1221.

In Example 10 above, it is shown that the starting metallocene having anLMCT band at 394 nm diminishes upon activation by HO-IBAO. Thedisappearance is accompanied by the growth of a broad absorption bandextended just beyond 700 nm. In Examples 15 et seq., use is made of theabsorbance at 600 nm for the purpose of monitoring stability. All UV-Vissamples have a same [Zr] concentration of 0.346 mM (2 umol Zr in 5 g oftoluene) in toluene.

EXAMPLE 15 Polymerization Using rac-ethylene bis(1-indenyl)zirconiumdimethyl pre-catalyst

A 15 ml high pressure mini-reactor was placed in a drybox and equippedwith a plastic anchor stirrer rotating at about 500 rpm.Hydroxyisobutylaluminoxane previously was made by hydrolyzing TIBA withone equivalent of water, and at the time of use in this polymerizationcontained about 450H groups per 100 Aluminum atoms. The metallocene,rac-ethylene bis(1-indenyl)zirconium dimethyl, was slurried in hexane inthe mini-reactor at ambient temperature, and thehydroxyisobutylaluminoxane was added thereto. The metallocene quicklydissolved to give a deep red solution. The Al/Zr molar ratio was 30:1.The mini-reactor was then charged with a portion of the catalystcomposition (0.2 micromoles Zr) and a 3 wt % TIBA solution in hexane(about 1 micromole Al). The reactor was then sealed and 6 ml of liquidpropylene was pressed into the reactor via a syringe pump to start thepolymerization. The temperature was quickly brought to 65° C. withinfour to six minutes. The polymerization was allowed for another 10minutes at 65° C., during which time all propylene was consumed. Afterdrying, 3.5 g of polypropylene was collected. The C₁₃-nmr of the polymershowed mmmm % equal to 84.5% and isotacticity index of 94.1%.

EXAMPLE 16 Stability of MET-A+HO-IBAO as an Isolated Product (Al/Zr=200)

To a suspension of dimethylsilylbis(2-methylindenyl)zirconium dimethyl(MET-A) (30 mg, 68 μmol) in 10 mL hexane was added a solution ofhydroxyisobutylaluminoxane (HO-IBAO) (13.2 g, 20 mmol Al) with stirring.Prior to the addition, the solution and the suspension were both cooledto −10° C. and after mixing, the resulting mixture was allowed to returnto room temperature. The metallocene gradually dissolved to give a deepred-brown solution. After 45 minutes of stirring, the solution wasstripped of volatiles under vacuum to initially give a foamy residuewhich was broken up by a spatula. Another 2 hours of pumping yielded acompletely dry brown powder which weighed 1.4 g. The brown solid wasstored in a drybox at room temperature, and was periodically sampled forstability determinations. Each sample was redissolved in toluene, andthe stability of the product was monitored by UV-Vis at 600 nm bymeasuring the metallocenium concentration of the respective redissolvedsamples. Samples were taken right after the isolated product had beendried, and after the isolated product had been stored for 6 days, 15days, and 39 days. The results, summarized in Table 1, show that themetallocenium concentration stayed constant throughout at least a 39-dayperiod. After one month of storage, the solid product was shown by amicro calorimetric test system to be highly active in ethylenepolymerization (50° C./50 psi in toluene).

TABLE 1 Change of UV-Vis Absorbance at 600 nm with Time Storage TimeProduct of Example 16 Right after drying 0.183  6 Days 0.181 15 Days0.187 39 Days 0.182

EXAMPLE 17 Stability of MET-A+HO-IBAO Product Dissolved in Toluene

A catalyst solution of Met-A and HO-IBAO with an Al/Zr molar ratio of100, was prepared. This solution was divided into two solutions, sampleA and B, whose UV-Vis spectra upon storage over time were recorded.Sample A was stored at ambient temperature in a drybox at all times.Sample B was stored at ambient temperature for the first 4.5 hours, andafter that was stored at −10° C. except during the spectra acquisitionwhich is done at room temperature. The results are summarized in Table2, in which the values marked with an asterisk are values of samplestaken from the product while the product was being stored at −10° C.

TABLE 2 Change of UV-Vis Absorbance at 600 nm with Time Storage TimeSample A Sample B 2 Hours 0.149 0.153 4.5 Hours 0.135 0.127 28 Hours0.101 0.126* 5 Days 0.081 0.124* 12 Days 0.064 0.121*

The results in Table 2 clearly show that the catalyst is unstable insolution at ambient room temperature but is rather stable in solution at−10° C.

EXAMPLE 18 Stability of MET-A+HO-IBAO as an Isolated Product (Al/Zr=50)

To a solution of HO-IBAO in hexane (6.78 g, 10.2 mmol Al) and 6.1 gtoluene was added solid MET-A (88 mg, 204 mmol) while the solution wascold. As a consequence of a lower Al/Zr ratio used in this Example,toluene was needed to dissolve the metallocene. After 23 minutes ofstirring at room temperature, the resulting dark brown solution wasstripped of volatiles in vacuo to give a foamy residue which was brokenup by a spatula. After a further 4 hours of pumping, 1.1 g of a brownpowder was isolated. The UV-Vis absorbances of this product at 600 nmwere 0.116 and 0.120 for solids sampled right after drying and after 6days of storage at ambient temperature, respectively.

EXAMPLE 19 Stability of MET-A+HO-IBAO as an Isolated Product (Al/Zr=300)

The procedure of Example 17 was followed except that MET-A (100 μmol)and HO-IBAO in hexane (30 mmol Al) were used and no additional hexanewas used. After drying, 3.2 g of a purple-brown solid was isolated. Theresults of the UV-Vis monitoring are summarized in Table 3.

TABLE 3 Change of UV-Vis Absorbance at 600 nm with Time Storage TimeProduct of Example 19 Right after drying 0.205 11 Days 0.178 24 Days0.177

EXAMPLE 20 Stability of MET-A+HO-IBAO as an Isolated Product (Al/Zr=60)

The HO-IBAO used in this Example is more freshly prepared than that inthe Example 18. As a consequence, no toluene was needed to dissolve themetallocene. Thus, the procedure in the Example 17 was followed exceptthat MET-A (200 mmol), HO-IBAO in hexane (12 mmol Al), and an additional4 g of hexane were used. After drying, 1.35 g of a purple-brown solidwere isolated. The results of the UV-Vis monitoring are summarized inTable 4.

TABLE 4 Change of UV-Vis Absorbance at 600 nm with Time Storage TimeProduct of Example 20 Right after drying 0.121  6 Days 0.122 20 Days0.132

For the following Examples 21-44, it will be noted that thehydroxyaluminoxane/silica materials were more difficult to characterizeusing DRIFTS. Without desiring to be bound by theory, it is believedthat the difficulties arise from the many types of OH groups, externalor internal, existing in silica which overlap with the OH groups ofhydroxyaluminoxane in the 3600-3800 cm−1 region in IR (the internal OHgroups of silica may be particularly troublesome since they cannot beeliminated by calcination or AlR₃ treatment). To overcome this problem,deuterated DO-IBAO was prepared by using D₂O in the hydrolysis of TIBAand the deuterated DO-IBAO was compared spectroscopically with HO-IBAOof identical composition. FIG. 8 shows the subtraction result of theDRIFTS spectra of the two materials; one bears OH (negative adsorptions,3600-3800 cm−1) and another OD (positive adsorptions, 2600-2800 cm−1).The subtracted spectrum eliminates the adsorption components from thesilica's OH groups and, thus, unambiguously proves the existence of theOH groups from IBAO.

Another problem encountered in characterizing thehydroxyaluminoxane/silica is the quantitative analysis of this class ofmaterial. Again without desiring to be bound to theory, it is believedthat the DRIFTS spectroscopy is inadequate in this respect because theheight of the adsorption (see FIG. 8) is somewhat sensitive to thematerial's surface area and its packing and flatness in the sampleholder. Consequently, a chemical method was designed for quantifying theOH groups. Again, the deuterated DO-IBAO proved to be useful. Treatmentof DO-IBAO/silica with an excess of benzylmagnesium chloride solutiongenerated mono-deuterated toluene (DCH₂Ph) which was then collected byvacuum distillation. FIG. 9 shows the H¹-nmr spectrum of such adistillate in CDCl₃. The great virtue of this method is believed to bethat the methyl group resonances of DCH₂Ph and toluene are sufficientlyresolved to allow easy integration. Toluene was present in thedistillate because the commercial benzyl Grignard reagent contained sometoluene and the surface OH of silica can also contribute to tolueneformation. With this method in hand, we were then able to study thestability of the OH groups on HO-IBAO/silica. Two samples ofDO-IBAO/silica were prepared for this study: Sample (1)—silica notreatment; IBAO with a hydrolysis ratio of 1.04, and Sample (2)—silicatreated with excess TEA; IBAO with a hydrolysis ratio of i. 16. Theloadings of the IBAO on silica were about 35% by weight for sample (1)and about 24% by weight for sample (2).

FIG. 8 shows the OD decay of the two samples and their comparison withthat of the soluble HO-IBAO (hydrolysis ratio 1.0). The sample (1), inwhich silica was not treated with AlR₃, has a decay profile that isquite similar to that of the soluble HO-IBAO except that its lifetime islonger at room temperature than that of soluble HO-IBAO at −10° C. Thesample (2) was hydrolyzed more, thereby having more than 10 OH groupsper 100 aluminums at the start. Strikingly, it has an OH decay profilethat is very different from the other two. It features an almost lineardecay and is a lot steeper, undoubtedly a result of its silicapre-treatment with TEA.

EXAMPLES 21-27 Synthesis of HO-IBAO/Silica

Preparations of all HO-IBAO/silica are summarized in Table 5. Silica,obtained from Crosfield (ES-70), was calcined either at 200° C. or 600°C. for 4 hours. Some of them were pre-treated with AlR₃ (dilute TEA orTIBA in hexane) at room temperature for one hour followed by filtration.

A typical procedure is as follows (Example 27): To a freshly preparedhydroxy IBAO solution in hexane (61.4 g, 87 mmol Al, hydrolysisratio=1.04) was added silica (15.0 g, calcined at 600° C., no AlR₃treatment) and stirred with a magnetic stir bar for 2 hours. After that,the slurry was allowed to settle. At this point, if there is anappreciable amount of supernatant, it may be separated from silica bydecant (see Table 5). In this example, there was no decant. Instead, theslurry was stripped of volatiles under vacuo, which was done slowly toprevent loss of fine silica particles. After drying, 23.0 g ofHO-IBAO/silica was collected, a 34.8% of IBAO loading. The ICP analysisof this solid showed 10.0 wt % Al. For deuterium-labeled DO-IBAO/silicasamples (Example 28), this procedure was followed except that D₂Oinstead of H₂O was used.

TABLE 5 Summary of HO-IBAO/silica preparation IBAO Silica Hydrol-reaction wt % calcine wt % ysis time de- loading Al Ex. (° C.) AlR₃ Alratio (hr) cant (wt %) (total) 21 600 TEA 3.0 1.18 16 no 23.8 10.1 22200 TIBA 3.2 1.18 16 yes 22.1 9.86 23 600 no 0 1.18 16 no 23.7 7.53 24600 no 0 1.18 4 yes 33.2 10.0 25 600 TEA 3.3 1.18 18 no 24.5 10.2 26 600TEA 3.3 1.18 4 yes 20.5 8.9 27 600 no 0 1.04 2 no 34.8 10.0

EXAMPLE 28 Quantifying the OD Groups in DO-IBAO/silica

For quantitative purposes, because silica was used as the carriermaterial, the use of deuterium-labeled DO-hydroxyaluminoxane/silica, andin this case DO-IBAO/silica, was preferred. Samples (1) and (2) werestored at room temperature in a dry box and were sampled periodicallyfor quantitative analysis (see FIG. 10). A typical procedure was asfollows. To the sample (1) DO-IBAO/silica (3.0 g, 11.1 mmol Al) inaround-bottomed flask was added a 2.0M solution of benzylmagnisiumchloride in THF (4.80 g). Additional THF (4.5 g) was added to aidstirring. The slurry was stirred for one hour at room temperature. Afterthat all volatiles were carefully vacuum-distilled off the solid residueat temperatures finally reaching 55° C. and collected in a liquidnitrogen trap. The amount of DCH₂Ph in the volatiles collected wasdetermined by H¹-nmr in CDCl₃. From that, the hydroxyl content wasdetermined to be 7.5 OD per 100 aluminums.

EXAMPLES 29-35 Preparation of Catalyst fromrac-dimethylsilylbis(2-methylindenyl)zirconium dimethyl Activated byHO-IBAO/silica

The synthesis of HO-IBAO activated silica-supported catalysts (see Table6 for summary) is exemplified as follows (Example 35): To a slurry ofHO-IBAO/silica (1.45 g) in hexane (12 ml) was added particulaterac-dimethylsilylbis(2-methylindenyl)zirconium dimethyl (86 mg) and themixture was allowed to stir at room temperature. After 75 minutes, theresulting deep brown slurry was filtered, solids washed several timeswith hexane until the filtrate was colorless, and suction dried for 10minutes to give a yellowish brown solid, weighing 1.42 g. The ICPanalysis of this solid showed 8.8 wt % Al and 1.0 wt % Zr, whichcorresponds to a Al/Zr molar ratio of 29.

TABLE 6 Properties of rac-dimethylsilylbis-(2-methylindenyl)- zirconiumdimethyl/HO-IBAO/silica catalysts Catalyst Example IBAO/silica wt % Alwt % Zr Al/Zr 29 21 10.2 0.46 53 30 22 8.1 0.54 51 31 23 8.4 0.43 41 3224 10.1 1.3 26 33 25 8.7 0.46 64 34 26 7.6 0.40 65 35 27 8.8 1.0 29

EXAMPLES 36-42

For each catalyst synthesized in Examples 29-35, polymerization ofpropylene was carried out in a 4-liter reactor charged with 2200 ml ofliquid propylene. At 65° C. with vigorous stirring, 1.0 ml of 5% TIBA(as scavenger) was injected into the reactor first, which was quicklyfollowed by another injection of the catalyst (110 mg slurried in 2 mlof dry hexane) to initiate polymerization. After one hour of reaction,the unreacted propylene was quickly vented. The results are summarizedin Table 7. No reactor fouling was seen in any of the polymerizations.

TABLE 7 Summary of Propylene Polymerization Results Polymer CatalystPolymer Catalyst Bulk Melting Point weight Yield Activity Density(onset/peak) MFI GPC Ex. Catalyst (mg) (g) (g/g/h) (g/ml) (° C.) (230°C./5 kg) Mw Mn Mw/Mn 36 29 154 396 2568 0.37 144.58/150.08 35.89 — — —37 30 206 15 73 0.28 — — — — — 38 31 165 367 2218 0.40 143.52/149.3939.73 253000 147000 1.72 39 32 164 247 1506 0.28 143.25/149.09 31.93300000 180000 1.67 40 33 160 170 1059 0.21 142.28/148.85 34.54 261000157000 1.66 41 34 161 39 243 0.15 — — — — — 42 35 41 185 4512 0.38143.01/148.85 28.47 267000 155000 1.72

EXAMPLE 43 Preparation of Catalyst from rac-ethylenebis(tetrahydroindenyl)zirconium dimethyl Activated by HO-IBAO/silica

The synthesis of this silica-supported catalyst was as described inexamples 29-35 except that HO-IBAO/silica (1.98 g), hexane (18 ml), andrac-ethylene bis(tetrahydroindenyl)zirconium dimethyl (160 mg) were usedand the mixture was allowed to stir at room temperature for 85 minutes.The product was a pink solid, weighing 1.97 g. The ICP analysis of thissolid showed 8.8 wt % Al and 1.3 wt % Zr, which corresponds to a Al/Zrmolar ratio of 23.

EXAMPLE 44 Ethylene Polymerization

The polymerization was carried out in a 4-liter reactor which wascharged with 1000 ml of isobutane and 40 ml hexene (pushed in by another500 ml of isobutene), sequentially. After stabilizing at 80° C., thereactor was pressurized with ethylene from 145 psig to 345 psig. Withvigorous stirring (600 rpm), 2.0 ml of 5% TIBA (as scavenger) wasinjected into the reactor first, which was quickly followed by aninjection of the catalyst from Example 43 (77.7 mg slurried in 3 ml ofdry hexane) to initiate polymerization. The reactor pressure wasmaintained at 315 psig by adding more make up ethylene. After one hourof reaction, unreacted ethylene and isobutane were quickly vented. Thepolyethylene fluff after drying weighed 198 g. No reactor fouling wasseen. Polymer properties: bulk density: 0.31 g/cc; M.P.: 109.17/121.09°C. (onset of second melt/peak). Melt flow index (190° C./5 kg) was toolow to measure (<0.1 g/10 min). Molecular weight via GPC was as follows:Mw=640,000, Mn=296,000, Mw/Mn=2.16.

While this invention has been specifically illustrated by reactionsbetween a metallocene and a hydroxyaluminoxane, it is to be understoodthat other suitable organometallic reactants having an appropriateleaving group can be employed. For example it is contemplated that theorganometallic complexes described in the following publications willform ionic compounds of this invention, provided that at least one ofthe halogen atoms bonded to the d-block or f-block metal atom isreplaced by a suitable leaving group such as a methyl, benzyl, ortrimethylsilylmethyl group:

Small, B. L.; Brookhart, M.; Bennett, A, M. A. J. Am. Chem. Soc. 1998,120, 4049.

Small, B. L.; Brookhart, M. J. Am. Chem. Soc. 1998, 120 7143.

Johnson, L. K.; Killian, C. M.; Brookhart, M. J. Am. Chem. Soc. 1995,117, 6414.

Killian, C. M.; Johnson, L. K; Brookhart, M. Organometallics 1997, 16,2005.

Killian, C. M.; Tempel, D. J.; Johnson, L. K.; Brookhart, M. J. Am.Chem. Soc. 1996, 118, 11664.

Johnson, L. K.; Mecking, S.; Brookhart, M. J. Am. Chem. Soc. 1996, 118,267.

It will now be appreciated that this invention is susceptible toconsiderable variation in its practice, as the invention providesnumerous advantages and features. Some of these advantages and featurescan be expressed in terms of the various embodiments of the inventionitself. The following comprises non-limiting examples of suchembodiments.

A1. A composition in the form of one or more individual solids, whichcomposition is formed from components comprised of (i) ahydroxyaluminoxane and (ii) a carrier material compatible with saidhydroxyaluminoxane and in the form of one or more individual solids,said composition having a reduced OH-decay rate relative to the OH-decayrate of (i).

A2. A composition according to A1 wherein (i) is supported on (ii).

A3. A composition according to A2 wherein (ii) consists essentially of aparticulate inorganic catalyst support material.

A4. A composition according to A3 wherein said inorganic catalystsupport material is comprised of anhydrous or substantially anhydrousparticles of silica, silica-alumina, or alumina.

A5. A composition according to A3 wherein said inorganic catalystsupport material consists essentially of a particulate porous calcinedsilica.

A6. A composition according to A3 wherein said inorganic catalystsupport material consists essentially of a particulate porous silicapretreated with an aluminum alkyl.

A7. A composition according to any of A1, A2, A3, A4, A5, or A6 whereinsaid hydroxyaluminoxane of (i) has less than 25 OH groups per 100aluminum atoms.

A8. A composition according to any of A1, A2, A3, A4, A5, or A6 whereinsaid hydroxyaluminoxane of (i) consists essentially ofhydroxyisobutylaluminoxane.

A9. A composition according to any of A1, A2, A3, A4, A5, or A6 whereinsaid composition is substantially insoluble in an inert organic solvent.

A10. A composition according to A9 wherein said hydroxyaluminoxane of(i) has less than 25 OH groups per 100 aluminum atoms.

A11. A composition according to A9 wherein said hydroxyaluminoxane of(i) consists essentially of hydroxyisobutylaluminoxane.

A12. A composition according to any of A1, A2, A3, A4, A5, or A6 whereinthe OH-decay rate of said composition is reduced relative to theOH-decay rate of (i) by a factor of at least 5.

A13. A composition according to A12 wherein said hydroxyaluminoxane of(i) has less than 25 OH groups per 100 aluminum atoms.

A14. A composition according to A12 wherein said hydroxyaluminoxane of(i) consists essentially of hydroxyisobutylaluminoxane.

A15. A composition according to A12 wherein said composition issubstantially insoluble in an inert organic solvent.

B1. A composition comprising a hydroxyaluminoxane supported on a solidsupport.

B2. A composition according to B1, wherein said composition ischaracterized by having an OH-decay rate which is reduced as compared tothe OH-decay rate of the hydroxyaluminoxane in a liquid or solidunsupported form.

B3. A composition according to B2 wherein the OH-decay rate of saidcomposition is reduced, as compared to that of said hydroxyaluminoxanein unsupported form, by a factor of at least 5.

B4. A composition according to any of B1, B2, or B3 wherein saidhydroxyaluminoxane has less than 25 hydroxyl groups per 100 aluminumatoms.

B5. A composition according to any of B1, B2, or B3 wherein saidhydroxyaluminoxane consists essentially of hydroxyisobutylaluminoxane.

B6. A composition according to any of B1, B2, or B3 wherein said solidsupport is a particulate inorganic catalyst support material.

B7. A composition according to B6 wherein said inorganic catalystsupport material is comprised of anhydrous or substantially anhydrousparticles of silica, silica-alumina, or alumina.

B8. A composition according to B6 wherein said inorganic catalystsupport material consists essentially of a particulate porous silicapretreated with an aluminum alkyl.

C1. A process comprising converting a hydroxyaluminoxane into acomposition in the form of one or more individual solids by bringingtogether (i) a hydroxyaluminoxane and (ii) a carrier material compatiblewith said hydroxyaluminoxane and in the form of one or more individualsolids, whereby the rate of OH-decay for said composition is reducedrelative to the rate of OH-decay of (i).

C2. A process according to C1 wherein (i) is converted into saidcomposition by supporting (i) on (ii).

C3. A process according to C2 wherein (ii) consists essentially of aparticulate inorganic catalyst support material.

C4. A process according to C3 wherein said inorganic catalyst supportmaterial is comprised of anhydrous or substantially anhydrous particlesof silica, silica-alumina, or alumina.

C5. A process according to C3 wherein said inorganic catalyst supportmaterial consists essentially of a particulate porous calcined silica.

C6. A process according to C3 wherein said inorganic catalyst supportmaterial consists essentially of a particulate porous silica pretreatedwith an aluminum alkyl.

C7. A process according to any of C1, C2, C3, C4, C5, or C6 wherein saidhydroxyaluminoxane of (i) has less than 25 OH groups per 100 aluminumatoms.

C8. A process according to C7 wherein said hydroxyaluminoxane of (i)consists essentially of hydroxyisobutylaluminoxane.

C9. A process according to any of C1, C2, C3, C4, CS, or C6 wherein theOH-decay rate of said composition is reduced, as compared to theOH-decay rate of (i), by a factor of at least 5.

C10. A process according to C9 wherein said hydroxyaluminoxane of (i)has less than 25 OH groups per 100 aluminum atoms.

C11. A process according to C10 wherein said hydroxyaluminoxane of (i)consists essentially of hydroxyisobutylaluminoxane.

C12. A process according to C9, wherein said composition is insoluble orsubstantially insoluble in an inert organic solvent.

D1. A supported activated catalyst composition formed by bringingtogether (A) a composition in the form of one or more individual solids,which composition is formed from components comprised of (i) ahydroxyaluminoxane and (ii) a carrier material compatible with saidhydroxyaluminoxane and in the form of one or more individual solids,said composition of (A) having a reduced OH-decay rate relative to theOH-decay rate of (i); and (B) a d- or f-block metal compound having atleast one leaving group on a metal atom thereof.

D2. A catalyst composition according to D1 wherein said d- or f-blockmetal compound is a Group 4 metal.

D3. A catalyst composition according to D1 wherein said d- or f-blockmetal compound is a metallocene.

D4. A catalyst composition according to D3 wherein the d- or f-blockmetal of said metallocene is at least one Group 4 metal.

D5. A catalyst composition according to D3 wherein said metallocenecontains two bridged or unbridged cyclopentadienyl-moiety-containinggroups.

D6. A catalyst composition according to D5 wherein the Group 4 metal ofsaid metallocene is zirconium.

D7. A catalyst composition according to D5 wherein the Group 4 metal ofsaid metallocene is titanium.

D8. A catalyst composition according to D5 wherein the Group 4 metal ofsaid metallocene is hafnium.

D9. A catalyst composition according to any of D1, D2, D3, D4, D5, D6,D7, or D8 wherein said hydroxyaluminoxane of (i) has less than 25hydroxyl groups per 100 aluminum atoms.

D10. A catalyst composition according to any of D1, D2, D3, D4, D5, D6,D7, or D8 wherein said hydroxyaluminoxane of (i) consists essentially ofhydroxyisobutylaluminoxane.

D11. A catalyst composition according to any of D1, D2, D3, D4, D5, D6,D7, or D8 wherein (ii) consists essentially of a particulate inorganiccatalyst support material.

D12. A catalyst composition according ton D1 wherein said catalystsupport material is comprised of anhydrous or substantially anhydrousparticles of silica, silica-alumina, or alumina.

D13. A catalyst composition according to D11 wherein said inorganiccatalyst support material consists essentially of a particulate porouscalcined silica.

D14. A catalyst composition according to D11 wherein said inorganiccatalyst support material consists essentially of a particulate poroussilica pretreated with an aluminum alkyl.

D15. A catalyst composition according to any of D1, D2, D3, D4, D5, D6,D7, or D8 wherein said composition in a dry or substantially dry stateis able to be maintained at a temperature in the range of about 10 toabout 60° C. for a period of at least 48 hours without losing fiftypercent (50%) or more of its catalytic activity.

E1. A process of preparing a supported activated catalyst, which processcomprises bringing together (A) a composition in the form of one or moreindividual solids formed by bringing together (i) a hydroxyaluminoxaneand (ii) a carrier material compatible with said hydroxyaluminoxane andin the form of one or more individual solids, whereby the rate ofOH-decay for said composition is reduced relative to the rate ofOH-decay of (i); and (B) a d- or f-block metal compound having at leastone leaving group on a metal atom thereof.

E2. A process according to E1 wherein (A) and (B) are brought togetherin an inert diluent.

E3. A process according to E1 wherein (A) and (B) are brought togetherin the absence of an inert diluent.

E4. A process according to E1 wherein said hydroxyaluminoxane of (i)consists essentially of hydroxyisobutylaluminoxane.

E5. A process according to E1 wherein said hydroxyaluminoxane of (i) hasless than 25 hydroxyl groups per 100 aluminum atoms.

E6. A process according to E1 wherein (ii) is a particulate inorganiccatalyst support material.

E7. A process according to E6 wherein said inorganic catalyst supportmaterial is comprised of anhydrous or substantially anhydrous particlesof silica, silica-alumina, or alumina.

E8. A process according to E6 wherein said inorganic catalyst supportmaterial consists essentially of a particulate porous calcined silica.

E9. A process according to E6 wherein said inorganic catalyst supportmaterial consists essentially of a particulate porous silica pretreatedwith an aluminum alkyl.

E10. A process according to E1 wherein said d- or f-block metal compoundis a metallocene.

E11. A process according to E10 wherein said at least one leaving groupof said metallocene is a methyl group.

E12. A process according to E10 wherein said metallocene contains twobridged or unbridged cyclopentadienyl-moiety-containing groups.

E13. A process according to E12 wherein the metal of said metallocene isa Group 4 metal.

E14. A process according to E13 wherein said Group 4 metal is zirconium.

E15. A process according to E13 wherein said Group 4 metal is titanium.

E16. A process according to E13 wherein said Group 4 metal is hafnium.

E17. A process according to any of E1, E2, E3, E4, E5, E6, E7, E8, E9,E10, E11, E12, E13, E14, E15, or E16, wherein said supported activatedcatalyst is recovered and maintained at a temperature in the range ofabout 10 to about 60° C. for a period of at least 48 hours withoutlosing fifty percent (50%) or more of its catalytic activity.

F1. An olefin polymerization process which comprises bringing togetherin a polymerization reactor or reaction zone (1) at least onepolymerizable olefin and (2) a supported activated catalyst compositionwhich is in accordance with any of C1, C2, C3, C4, C5, C6, C7, or C8.

F2. An olefin polymerization process according to F1 wherein thepolymerization process is conducted as a gas-phase polymerizationprocess.

F3. An olefin polymerization process according to F1 wherein thepolymerization process is conducted in a liquid phase diluent.

F4. An olefin polymerization process according to F1 wherein thepolymerization process is conducted as a fluidized bed process.

F5. An olefin polymerization process according to F1 wherein saidhydroxyaluminoxane of (i) has less than 25 hydroxyl groups per 100aluminum atoms.

F6. An olefin polymerization process according to F5 wherein thepolymerization process is conducted as a gas-phase polymerizationprocess.

F7. An olefin polymerization process according to F5 wherein thepolymerization process is conducted in a liquid phase diluent.

F8. An olefin polymerization process according to F5 wherein thepolymerization process is conducted as a fluidized bed process.

F9. An olefin polymerization process according to F1 wherein saidhydroxyaluminoxane of (i) consists essentially ofhydroxyisobutylaluminoxane.

F10. An olefin polymerization process according to F1 wherein (ii)consists essentially of a particulate inorganic catalyst supportmaterial.

F11. An olefin polymerization process according to F10 wherein saidcatalyst support material is comprised of anhydrous or substantiallyanhydrous particles of silica, silica-alumina, or alumina.

F12. An olefin polymerization process according to F10 wherein saidinorganic catalyst support material consists essentially of aparticulate porous calcined silica.

F13. An olefin polymerization process according to F10 wherein saidinorganic catalyst support material consists essentially of aparticulate porous silica pretreated with an aluminum alkyl.

F14. An olefin polymerization process according to F10 wherein thepolymerization process is conducted as a gas-phase polymerizationprocess.

F15. An olefin polymerization process according to F10 wherein thepolymerization process is conducted in a liquid phase diluent.

F16. An olefin polymerization process according to F10 wherein thepolymerization process is conducted as a fluidized bed process.

G1. A catalyst composition formed by bringing together (A) ahydroxyaluminoxane and (B) rac-ethylene bis(1-indenyl)zirconiumdimethyl.

G2. A catalyst composition according to G1 wherein (A) and (B) arebrought together in an inert diluent.

G3. A catalyst composition according to G1 wherein (A) and (B) arebrought together in the absence of an inert diluent.

G4. A catalyst composition according to any of G1, G2, or G3 whereinsaid hydroxyaluminoxane of (A) has less than 25 hydroxyl groups per 100aluminum atoms.

G5. A catalyst composition according to G4 wherein said composition in adry state is able to be maintained at a temperature in the range ofabout 10 to about 60° C. for a period of at least 48 hours withoutlosing fifty percent (50%) or more of its catalytic activity.

G6. A catalyst composition according to any of G1, G2, or G3 whereinsaid hydroxyaluminoxane of (A) consists essentially ofhydroxyisobutylaluminoxane.

G7. A catalyst composition according to G6 wherein said composition in adry state is able to be maintained at a temperature in the range ofabout 10 to about 60° C. for a period of at least 48 hours withoutlosing fifty percent (50%) or more of its catalytic activity.

G8. A catalyst composition according to any of G1, G2, or G3 whereinsaid hydroxyaluminoxane of (A) is supported on a particulate inorganiccatalyst support material.

G9. A catalyst composition according to G8 wherein said inorganiccatalyst support material is comprised of anhydrous or substantiallyanhydrous particles of silica, silica-alumina, or alumina.

G10. A catalyst composition according to G8 wherein said inorganiccatalyst support material consists essentially of a particulate poroussilica pretreated with an aluminum alkyl.

G11. A catalyst composition according to G8 wherein said composition ina dry state is able to be maintained at a temperature in the range ofabout 10 to about 60° C. for a period of at least 48 hours withoutlosing fifty percent (50%) or more of its catalytic activity.

H1. A process for the production of a supported hydroxyaluminoxane whichcomprises bringing together (i) an aluminum alkyl in an inert solvent,(ii) a water source, and (iii) a carrier material, underhydroxyaluminoxane-forming reaction conditions.

H2. A process according to H1 wherein said aluminum alkyl is atrialkylaluminum.

H3. A process according to H1 wherein said water source consistsessentially of free water.

H4. A process according to H1 wherein said water source consistsessentially of a hydrated inorganic salt or un-dehydrated silica

H5. A process according to H1 wherein said carrier material is a solidsupport.

H6. A process according to H5 wherein said solid support is aparticulate inorganic catalyst support material.

H7. A process according to H6 wherein said inorganic catalyst supportmaterial is comprised of anhydrous or substantially anhydrous particlesof silica, silica-alumina, or alumina.

H8. A process according to H6 wherein said inorganic catalyst supportmaterial consists essentially of a particulate porous calcined silica.

H9. A process according to H6 wherein said inorganic catalyst supportmaterial consists essentially of a particulate porous silica pretreatedwith an aluminum alkyl.

J1. A method of forming an olefin polymerization catalyst, which methodcomprises feeding into a vessel (A) a hydroxyaluminoxane and (B) a d- orf-block metal compound in proportions such that an active olefinpolymerization catalyst is formed.

J2. A method according to J1 wherein the hydroxyaluminoxane is fed inthe form of a solution formed from the hydroxyaluminoxane in an inertsolvent or in a liquid polymerizable olefinic monomer, or both.

J3. A method according to J1 wherein the hydroxyaluminoxane is fed inthe form of a slurry formed from the hydroxyaluminoxane in an inertdiluent or in a liquid polymerizable olefinic monomer.

J4. A method according to J1 wherein the hydroxyaluminoxane is fed inthe form of unsupported solid particles.

J5. A method according to J1 wherein the hydroxyaluminoxane is fed inthe form of one or more solids on a carrier material.

J6. A method according to J1 wherein the hydroxyaluminoxane is fed inthe form of (i) a solution formed from the hydroxyaluminoxane in aninert solvent or in a liquid polymerizable olefinic monomer, or both;(ii) a slurry formed from the hydroxyaluminoxane in an inert diluent orin a liquid polymerizable olefinic monomer; (iii) unsupported solidparticles; or (iv) one or more solids on a carrier material; or (v) anycombination of two or more of (i), (ii), (iii), and (iv).

J7. A method according to any of J1, J2, J3, J4, J5, or J6 wherein thed- or f-block metal compound is fed in the form of undiluted solids orliquid.

J8. A method according to any of J1, J2, J3, J4, J5, or J6 wherein thed- or f-block metal compound is fed in the form of a solution or slurryof the d- or f-block metal compound in an inert solvent or diluent, orin a liquid polymerizable olefinic monomer, or in a mixture of any ofthese.

K1. In a process for the catalytic polymerization of at least one olefinin a reaction vessel or reaction zone, the improvement which comprisesintroducing into the reaction vessel or reaction zone catalystcomponents comprising (A) a hydroxyaluminoxane and (B) a d- or f-blockmetal compound, in proportions such that said at least one olefin ispolymerized.

K2. The improvement according to K1 wherein the hydroxyaluminoxane isintroduced in the form of a solution formed from the hydroxyaluminoxanein an inert solvent or in a liquid form of said at least one olefin, orboth.

K3. The improvement according to K1 wherein the hydroxyaluminoxane isintroduced in the form of a slurry formed from the hydroxyaluminoxane inan inert diluent or in a liquid form of said at least one olefin.

K4. The improvement according to K1 wherein the hydroxyaluminoxane isintroduced in the form of unsupported solid particles.

K5. The improvement according to K1 wherein the hydroxyaluminoxane isintroduced in the form of one or more solids on a carrier material.

K6. The improvement according to K5 wherein the one or more solids onthe carrier material are in an inert viscous liquid.

K7. The improvement according to K1 wherein the hydroxyaluminoxane isintroduced in the form of (i) a solution formed from thehydroxyaluminoxane in an inert solvent or in a liquid form of said atleast one olefin, or both; (ii) a slurry formed from thehydroxyaluminoxane in an inert diluent or in a liquid form of said atleast one olefin; (iii) unsupported solid particles; or (iv) one or moresolids on a carrier material; or (v) any combination of two or more of(i), (ii), (iii), and (iv).

K8. The improvement according to any of K1, K2, K3, K4, K5, K7 whereinthe d- or f-block metal compound is introduced in the form of undilutedsolids or liquid.

K9. The improvement according to any of K1, K2, K3, K4, K5, K6, or K7wherein the d- or f-block metal compound is introduced in the form of asolution or slurry of the d- or f-block metal compound in an inertsolvent or diluent, or in a liquid form of said at least one olefin, orin a mixture of any of these.

The materials referred to by chemical name or formula anywhere in thespecification or claims hereof are identified as ingredients to bebrought together in connection with performing a desired operation or informing a mixture to be used in conducting a desired operation.Accordingly, even though the claims hereinafter may refer to substancesin the present tense (“comprises”, “is”, etc.), the reference is to thesubstance, as it existed at the time just before it was first contacted,blended or mixed with one or more other substances in accordance withthe present disclosure. The fact that a substance may lose its originalidentity through a chemical reaction, complex formation, solvation,ionization, or other transformation during the course of contacting,blending or mixing operations, if done in accordance with the disclosurehereof and with the use of ordinary skill of a chemist and common sense,is within the purview and scope of this invention.

Each and every patent or other publication referred to in any portion ofthis specification is incorporated in full into this disclosure byreference, as if fully set forth herein.

The foregoing description is not intended to limit, and should not beconstrued as limiting, the invention to the particular exemplificationspresented hereinabove. Rather, what is intended to be covered is as setforth in the ensuing claims and the equivalents thereof permitted as amatter of law.

What is claimed is:
 1. A composition in the form of one or moreindividual solids, which composition is formed from components comprisedof (i) a hydroxyaluminoxane and (ii) a carrier material compatible withsaid hydroxyaluminoxane and in the form of one or more individualsolids, wherein (i) is supported on (ii), wherein (ii) consistsessentially of a particulate inorganic catalyst support material, andwherein said inorganic catalyst support material consists essentially ofa particulate porous calcined silica or a particulate porous silicapretreated with an aluminum alkyl.
 2. A composition in the form of oneor more individual solids, which composition is formed from componentscomprised of (i) a hydroxyaluminoxane and (ii) a carrier materialcompatible with said hydroxyaluminoxane and in the form of one or moreindividual solids, wherein said hydroxyaluminoxane of (i) has less than25 OH groups per 100 aluminum atoms.
 3. A composition according to claim2 wherein (i) is supported on (ii), and wherein (ii) consistsessentially of a particulate inorganic catalyst support material.
 4. Acomposition according to claim 3 wherein said inorganic catalyst supportmaterial consists essentially of a particulate porous calcined silica ora particulate porous silica pretreated with an aluminum alkyl.
 5. Acomposition in the form of one or more individual solids, whichcomposition is formed from components comprised of (i) ahydroxyaluminoxane and (ii) a carrier material compatible with saidhydroxyaluminoxane and in the form of one or more individual solids,wherein said hydroxyaluminoxane of (i) consists essentially ofhydroxyisobutylaluminoxane.
 6. A composition according to claim 5wherein (i) is supported on (ii), and wherein (ii) consists essentiallyof a particulate inorganic catalyst support material.
 7. A compositionaccording to claim 6 wherein said inorganic catalyst support materialconsists essentially of a particulate porous calcined silica or aparticulate porous silica pretreated with an aluminum alkyl.
 8. Acomposition in the form of one or more individual solids, whichcomposition is formed from components comprised of (i) ahydroxyaluminoxane and (ii) a carrier material compatible with saidhydroxyaluminoxane and in the form of one or more individual solids,wherein (i) is supported on (ii), wherein the OH-decay rate of saidcomposition is reduced relative to the OH-decay rate of (i) by a factorof at least 5, and wherein said hydroxyaluminoxane of (i) has less than25 OH groups per 100 aluminum atoms.
 9. A composition according to claim8, wherein said hydroxyaluminoxane of (i) consists essentially ofhydroxyisobutylaluminoxane.
 10. A composition according to claim 8wherein (ii) consists essentially of a particulate inorganic catalystsupport material.
 11. A composition according to claim 10 wherein saidhydroxyaluminoxane of (i) consists essentially ofhydroxyisobutylaluminoxane.
 12. A composition according to claim 10wherein said inorganic catalyst support material consists essentially ofa particulate porous calcined silica or a particulate porous silicapretreated with an aluminum alkyl.
 13. A composition according to claim12 wherein said hydroxyaluminoxane of (i) consists essentially ofhydroxyisobutylaluminoxane.